TWI374119B

TWI374119B - Process for synthesizing cubic metallic nanoparticles in the presence of two reducing agents

Info

Publication number: TWI374119B
Application number: TW097111128A
Authority: TW
Inventors: Cecile Thomazeau; Clement Sanchez; Cedric Boissiere; Laure Bisson
Original assignee: IFP Energies Nouvelles
Priority date: 2007-03-30
Filing date: 2008-03-27
Publication date: 2012-10-11
Also published as: CN101646491A; TW200902449A; US8652232B2; WO2008132314A3; SA08290175B1; DK2134468T3; CN101646491B; FR2914200B1; WO2008132314A2; EP2134468B1; US20100280296A1; EP2134468A2; FR2914200A1

Description

1374119 九、發明說明：【發明所屬之技術領域】本發明係關於—種製備沈積於載體上之立方金屬夺米粒子的方法。該等經負載奈米粒子可用作催化劑，尤其用以進行氫化過程。【先前技術】1374119 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for preparing cubic metal-grained particles deposited on a carrier. The supported nanoparticles can be used as a catalyst, especially for carrying out the hydrogenation process. [Prior Art]

金屬，尤其過渡金屬因其活化諸如烴、氫、氧或一氧化碳之某些分子之能力巾已被使用乡年。金^對彼等分子之催化特性已成.為大量研究之焦點，該等研究已說明其視金屬而定之多功能性、所用條件以及其物理化學特徵。化子吸附活化現象，亦即受反應物之吸附及該等反應物與金屬粒子之間的化學相互作用支配之現象，視所暴露之金屬表面的物理化學特性而定。金屬粒子之尺寸及該粒子表面原子之配位為當產生具有最優化學吸附特性之催化別（亦即具有吸附反應物且與該等反應物化學相互作用之倉<=*力的催化劑）時必須考慮之兩個特徵。金屬粒子之尺寸通常視預計應用而定加以選擇。已知金屬奈米粒子能夠呈現各種穩定形態，此視構成其之原子數目或與其環境（亦即，例如與反應性氣氛）之化學相互作用而定。用於異質催化之金屬粒子具有具顯著各向同性特徵之形態’呈現視組成粒子之原子數目而定的幾何 $態。此等幾何形態包括對於尺寸通常小於約丨〇埃〇埃 =]Q* 1 0 、之小粒子而言的二十面體形態，及對於大粒子而舌之截頂立方八面體形態。】29699.doc 1374119 本發明之一目標在於提供—種製備沈積於載體上之金屬，丁、米粒子以便控制此等奈米粒子之形態且尤其以便允許製備具有立方形態（亦即形態因子F在範圍〇78至〇81内）之經負載奈米粒子的方法。合成奈米粒子之某些方法已為熟習此項技術者所熟知。熟習此項技術者瞭解於有機介質中（例如於醇或多元醇中）以溶液狀態合成立方形態之奈米粒子的方法，其中奈米粒子之生長可藉由單—步驟㈣擇性試劑之吸附控制。還原通常於⑽下，亦即於有機介質之沸點下進行，且有機相同時充當選擇性吸附試劑（通常為聚合物）之溶劑及金屬前驅體之還原劑。該等方法已於WUeyB，Sun γ，Μ3ρ B’ Xia Y，Chem Em· J，2005, 1 1，454中描述。舉例而言’ 邊長為約170 nm之銀奈米粒子係藉由在16〇t下於聚乙烯吡咯啶酮存在下用乙二醇還原鹽AgN〇3來形成。該等方法有使用為弱還原劑且必須於高溫下活化之有機化合物的缺點。Metals, especially transition metals, have been used for years because of their ability to activate certain molecules such as hydrocarbons, hydrogen, oxygen or carbon monoxide. The catalytic properties of gold^ for their molecules have become the focus of much research. These studies have demonstrated their versatility, conditions and physicochemical characteristics depending on the metal. The phenomenon of adsorbent activation, that is, the adsorption of reactants and the chemical interaction between the reactants and the metal particles, depends on the physicochemical properties of the exposed metal surface. The size of the metal particles and the coordination of the atoms on the surface of the particles are the catalysts that produce the optimal chemisorption characteristics (ie, the catalysts that have adsorbed reactants and chemically interact with the reactants). Two characteristics must be considered when considering. The size of the metal particles is usually chosen depending on the intended application. It is known that metal nanoparticles can assume various stable forms depending on the number of atoms or the chemical interaction with their environment (i.e., with respect to a reactive atmosphere). The metal particles used for heterogeneous catalysis have a geometrical state in which the morphology of the isotropic features is present depending on the number of atoms of the constituent particles. Such geometric forms include icosahedral morphology for small particles of size generally less than about 丨〇〇 = =] Q* 1 0 , and truncated cubic octahedron morphology for large particles. 29699.doc 1374119 One object of the present invention is to provide a metal, butyl, and rice particle deposited on a support to control the morphology of such nanoparticles and, in particular, to allow for the preparation of a cubic form (ie, a morphological factor F) The method of loading nanoparticles in the range of 〇78 to 〇81). Certain methods of synthesizing nanoparticle are well known to those skilled in the art. Those skilled in the art are aware of a method for synthesizing cubic nanoparticles in a solution state in an organic medium (for example, in an alcohol or a polyol), wherein the growth of the nanoparticles can be carried out by a single-step (four) selective reagent adsorption. control. The reduction is usually carried out under (10), i.e., at the boiling point of the organic medium, and, when organically equivalent, acts as a solvent for the selective adsorption reagent (usually a polymer) and a reducing agent for the metal precursor. Such methods are described in WUey B, Sun γ, Μ 3ρ B’ Xia Y, Chem Em J, 2005, 1, 1,454. For example, silver nanoparticles having a side length of about 170 nm are formed by reducing the salt AgN〇3 with ethylene glycol in the presence of polyvinylpyrrolidone at 16 Torr. These methods have the disadvantage of using organic compounds that are weak reducing agents and must be activated at elevated temperatures.

於有機介質中以溶液狀態合成之方法包括可藉由選擇認為具有有利於還原及受控生長之配位體的金屬前驅體來控制金屬奈米粒子之生長的一些方法，在此等合成方法中，該荨有機金屬前驅體之分解係如Chaudret等人，C RThe method of synthesizing in a solution state in an organic medium includes some methods for controlling the growth of metal nanoparticles by selecting a metal precursor which is considered to have a ligand which is advantageous for reduction and controlled growth, in which the synthesis method , the decomposition of the cerium organometallic precursor such as Chaudret et al., CR

Chimie，6，2003，1019-1034 所述進行。如 Margeat 0,Chimie, 6, 2003, 1019-1034. Like Margeat 0,

Dumestre F, Amiens C, Chaudret B, Lecante P, Respaud P, Respaud M, Progress in solid state chemistry, 33 (2-4)，71， 2005中所述，可引用之一實例為使用長碳鏈胺及酸配位體 129699.doc 1374119 來合成鐵奈米立方體。除於有機介質中進行之溶液合成方法外，亦存在在水性介質中之合成方法。術語"水性介質”意謂包含至少一個主要水相及可能之有機相之介質。更特定言之，本發明係關於此等水性介質合成方法之領域。已知將使用界面活性劑之水性介質合成方法用於製備具有各向同性奈米粒子之催化劑。B Veisz& z Kiraii，Dumestre F, Amiens C, Chaudret B, Lecante P, Respaud P, Respaud M, Progress in solid state chemistry, 33 (2-4), 71, 2005, one example may be cited using long carbon chain amines and The acid ligand 129699.doc 1374119 was used to synthesize the Tennemid cube. In addition to solution synthesis methods carried out in organic media, there are also synthetic methods in aqueous media. The term "aqueous medium" means a medium comprising at least one major aqueous phase and possibly an organic phase. More particularly, the invention relates to the field of methods for synthesizing such aqueous media. It is known to synthesize aqueous media using surfactants. The method is used to prepare a catalyst having isotropic nanoparticles. B Veisz & z Kiraii,

Langmuir 2003, 19, 4817之文章描述立方八面體形態之各向同性鈀奈米粒子之合成。美國專利US_A 4 714 693描述一種藉由與金屬前驅體相互作用之微胞的形成、接著沈積及還原來合成經負載奈米粒子的方法。The article by Langmuir 2003, 19, 4817 describes the synthesis of isotropic palladium nanoparticles in cubic octahedral morphology. US Patent No. 4,714,693 describes a method of synthesizing supported nanoparticle by formation, subsequent deposition and reduction of micelles that interact with a metal precursor.

具有文控形態之奈米粒子亦可藉由使離子、分子、聚合物或界面活性劑選擇性吸附於金屬之某些結晶表面上而於水性介質中合成。藉由添加函離子來控制形態亦已由 Filankembo等人（J Phys Chem B，2003, 1〇7, 7492)觀察到。此等合成方法僅僅用於銅、銀及金。在利用聚合物於金屬之某些結晶表面上之選擇性吸附的水性介質合成方法之領域中，美國專利US_A_6 〇9〇 858描述一種用以使用穩定劑產生具有特定形態之過渡金屬之膠態奈米粒子的方法’該方法包含將金屬前驅體與穩定劑之混合物溶解於水性溶液中，接著在單一還原劑（亦即氫）存在下還原，此不能以最Μ式控制形態。然而，此方法可能僅產生約60%比例之始立方體⑽州應r，El_Sayed μ Α，Nanoletters, 2004，4 (7) 1343) 〇 129699.doc 1374119 此受控生長方法亦可藉由在第一步驟中合成各向同性奈米粒子’接著使用該等奈米粒子作為在選擇性吸附劑及合適還原劑存在下生長之晶種來達成。如Sau Τ K，Murphy C J，J Am Chem Soc，2004，126, 8648所述，此使用兩種還原劑之方法使得金之立方奈米粒子能夠得以合成β 【發明内容】本發明係關於一種製備立方金屬奈米粒子之方法，其至少包含下列步驟：Nanoparticles having a textual morphology can also be synthesized in an aqueous medium by selective adsorption of ions, molecules, polymers or surfactants to certain crystalline surfaces of the metal. Controlling morphology by the addition of a functional ion has also been observed by Filankembo et al. (J Phys Chem B, 2003, 197, 7492). These synthetic methods are only used for copper, silver and gold. In the field of aqueous media synthesis processes utilizing the selective adsorption of polymers onto certain crystalline surfaces of metals, U.S. Patent No. 5,858 describes a colloidal naphthalene used to produce transition metals having a particular morphology using stabilizers. Method of rice particles 'This method comprises dissolving a mixture of a metal precursor and a stabilizer in an aqueous solution, followed by reduction in the presence of a single reducing agent (i.e., hydrogen), which does not control the morphology in the most sturdy manner. However, this method may only produce about 60% of the initial cube (10) state should be r, El_Sayed μ Α, Nanoletters, 2004, 4 (7) 1343) 〇 129699.doc 1374119 This controlled growth method can also be used in the first The synthesis of isotropic nanoparticles in the step is followed by the use of the nanoparticles as seed crystals grown in the presence of a selective adsorbent and a suitable reducing agent. As described in Sau Τ K, Murphy CJ, J Am Chem Soc, 2004, 126, 8648, this method of using two reducing agents enables gold cubic nanoparticles to be synthesized. [Invention] The present invention relates to a preparation. A method of cubic metal nanoparticle, comprising at least the following steps:

a) 製備至少一種水性溶液，其含有至少一種選自元素週期表第VIII族金屬之金屬的至少一個來源' 至少一種還原劑R1及至少一種穩定劑； b) 於嚴格高於70°C且小於或等於8〇。(：之溫度下製備至少一種水性溶液，其含有至少一種選自元素週期表第νιπ族金屬之金屬的至少一個來源及至少一種穩定劑； c) 在至少一種還原劑R2存在下將步驟a)中獲得之該水性溶液之至少一部分與步驟b)中獲得之該水性溶液混合以獲得呈立方形態之金屬奈米粒子，其佔所形成之金屬奈米粒子之全部數量的至少70數目〇/〇 ; 句使源自步驟c)之該等金屬奈米粒子沈積於載體上。根據本發明之方法製備的經負載金屬奈米粒子（其中至少70數目％呈立方形態）被用作選擇性氫化不飽和烴之催化齊J在此類應用中，令人驚訝地顯示此類催化劑比基於金屬奈米粒子之經負載催化劑(其中為立方形態之彼等粒子佔小於70數目％)更具活性。亦已顯示使用本發明之方法製 129699.doc 1374119 備之催化劑因促使形成不利於飽和產物之單不飽和產物而對單不飽和產物更具選擇性，且其對一種單不飽和異構體比對另一種單不飽和異構體更具選擇性。【實施方式】本發明係關於一種製備立方金屬奈米粒子之方法，其至少包含下列步驟：a) preparing at least one aqueous solution containing at least one source selected from the group consisting of metals of Group VIII metals of the Periodic Table of the Elements, at least one reducing agent R1 and at least one stabilizer; b) being strictly above 70 ° C and less than Or equal to 8〇. (at a temperature of at least one aqueous solution containing at least one source selected from the group consisting of metals of the group νιπ metal of the periodic table and at least one stabilizer; c) step a) in the presence of at least one reducing agent R2 At least a portion of the aqueous solution obtained in the step b) is mixed with the aqueous solution obtained in the step b) to obtain a metal nanoparticle in a cubic form, which accounts for at least 70 of the total amount of the formed metal nanoparticles. The sentence causes the metal nanoparticles derived from step c) to be deposited on the support. Supported metal nanoparticles prepared according to the process of the invention wherein at least 70% by weight is in a cubic form are used as catalysts for the selective hydrogenation of unsaturated hydrocarbons. In such applications, such catalysts have surprisingly been shown. It is more active than supported catalysts based on metallic nanoparticles, in which the particles in cubic form account for less than 70% by number. It has also been shown that the catalyst prepared by the process of the present invention, 129,699.doc 1374119, is more selective for monounsaturated products by promoting the formation of monounsaturated products which are detrimental to saturated products, and its ratio to monounsaturated isomers. More selective for another monounsaturated isomer. [Embodiment] The present invention relates to a method of preparing cubic metal nanoparticles, which comprises at least the following steps:

a) 製備至少一種水性溶液，其含有至少一種選自元素週期表第VIII族金屬之金屬的至少一個來源、至少一種還原劑R1及至少一種穩定劑； b) 於嚴格咼於70°C且小於或等於80。〇之溫度下製備至少一種水性溶液，其含有至少一種選自元素週期表第¥111族金屬之金屬的至少一個來源及至少一種穩定劑； C)在至少一穢還原劑R2存在下將步驟a)中獲得之該水性溶液之至少一部分與步驟b)中獲得之該水性溶液混合以獲知·呈立方形態之金屬奈米粒子，其佔所形成之金屬奈米粒子之全部數量的至少70數目％ ; d)使源自步驟c)之該等金屬奈米粒子沈積於載體上。本發明之方法導致產生金屬奈米粒子，其中至少7〇數目 %呈立方形態。該等立方金屬奈米粒子係由至少一種選自元素週期表第vm族金屬之金屬構成。使用熟習此項技術者已知之術語，該等使用本發明之方法製備之立方金屬奈米粒子呈立方體之形態或呈截頂立方體之形態。當奈米粒子呈立方體之形態時，立方體之各面的相鄰邊形成9〇〇之角度。當奈米粒子呈戴頂立方體之形態時，立方體之各面 129699.doc 1374119a) preparing at least one aqueous solution containing at least one source selected from the group consisting of metals of Group VIII metals of the Periodic Table of the Elements, at least one reducing agent R1 and at least one stabilizer; b) being strictly at 70 ° C and less than Or equal to 80. Preparing at least one aqueous solution containing at least one source selected from the group consisting of metals of Group 111 of the Periodic Table of the Elements and at least one stabilizer at a temperature of ;; C) step a in the presence of at least one hydrazine reducing agent R2 And at least a portion of the aqueous solution obtained in step b) is mixed with the aqueous solution obtained in step b) to obtain a metal nanoparticle in a cubic form, which accounts for at least 70% by number of the total amount of the formed metal nanoparticles. d) depositing the metal nanoparticles derived from step c) on a support. The process of the invention results in the production of metallic nanoparticles wherein at least 7 % of the number is in cubic form. The cubic metal nanoparticles are composed of at least one metal selected from the group Vm metal of the periodic table. The terminology known to those skilled in the art is such that the cubic metal nanoparticles prepared by the method of the present invention are in the form of a cube or in the form of a truncated cube. When the nanoparticles are in the form of a cube, the adjacent sides of the faces of the cube form an angle of 9 。. When the nanoparticles are in the form of a topped cube, the faces of the cube are 129699.doc 1374119

:相鄰邊之間形成的角度不同於9〇。，此係因為由該等邊形成之轉角被截頂。使用本發明之方法製備之立方金屬太水軚子具有在範圍0.78至〇.81内之形態因子。當形態因: 為0.78時，立方金屬奈米粒子呈立方體之形態。當形態因 △為0.81時，金屬奈米粒子呈具有邊&之截頂立方體之形態’該等邊之截斷各自等於a/4。邊3具有m78且小於 =81之开i態因子的立方金屬纟米粒子呈截頂立方體之形其中該等邊之截斷各自小於a/4。該形態因子係由式 F=(4*n*S)/P2定義，S為在以透射電子顯微術表徵之二維平面上量測之粒子的表面積，P為在同一平面上量測之粒子的周長。粒子之表面積對應於在TEM表徵平面上檢視到的立方奈米粒子之面的表面積且粒子之周長對應於在tem表徵平面上檢視到的立方奈米粒子之面的周長。如上文所定義之形態因子F係有利地根據使用C〇ster M，chermant j [: The angle formed between adjacent sides is different from 9〇. This is because the corner formed by the equilateral edges is truncated. The cubic metal scorpion prepared using the method of the present invention has a morphological factor in the range of 0.78 to 〇.81. When the morphology is: 0.78, the cubic metal nanoparticles are in the form of a cube. When the form factor Δ is 0.81, the metal nanoparticles are in the form of truncated cubes having sides & the cutoffs of the sides are each equal to a/4. The cubic metal nanoparticles having edge i having an open state factor of m78 and less than =81 are in the shape of a truncated cube in which the cutoffs of the equal sides are each smaller than a/4. The morphological factor is defined by the formula F = (4 * n * S) / P2, S is the surface area of the particles measured on a two-dimensional plane characterized by transmission electron microscopy, and P is measured on the same plane. The perimeter of the particle. The surface area of the particles corresponds to the surface area of the face of the cubic nanoparticles examined on the TEM representation plane and the perimeter of the particles corresponds to the perimeter of the face of the cubic nanoparticles examined on the tem surface. The morphological factor F as defined above is advantageously based on the use of C〇ster M,chermant j [

Precis d'analyse d'images [Manual of image analysis], CNRS，1985所述之方法藉由透射電子顯微術進行之量測來計算。形態因子F在範圍0.78至0.81内之立方金屬奈米粒子之比例係由使用熟習此項技術者已知之統計計數規則的統計分析來測定》詳言之，在代表藉由TEM分析之樣品之全部的至少2 0 0個奈米粒子之群體内進行對立方奈米粒子之數目的計數。統計.計數通常直接於TEM影像上進行。使用本發明之方法製備之金屬奈米粒子（其中至少7〇數目％由立方金屬奈米粒子形成）係由至少一種選自元素週期 129699.doc 1374119 表第VIII族金屬之金屬構成。第VIII族金屬較佳係選自鎳、鈷、鐵、釕、鉑、鈀及銥，非常較佳地為選自鈷、鎳、鉑及鈀且更佳為選自鈀。該等使用本發明之方法製備之金屬奈米粒子（其中至少70數目。/。由立方金屬奈来粒子形成）有利地係由至少兩種金屬構成，其中至少一者係選自元素週期表第VIII族金屬，第二種金屬較佳係選自元素週期表第VIII族及第IB族金屬，非常較佳地為選自第IB族金屬且更佳為選自銀及金。The method described in Precis d'analyse d'images [Manual of image analysis], CNRS, 1985 is calculated by measurement by transmission electron microscopy. The ratio of cubic metal nanoparticles having a morphological factor F in the range of 0.78 to 0.81 is determined by statistical analysis using statistical counting rules known to those skilled in the art, in detail, representing all of the samples analyzed by TEM. The number of cubic nanoparticles is counted in a population of at least 200 nanoparticles. Statistics. Counting is usually performed directly on the TEM image. The metal nanoparticles prepared by the method of the present invention (at least 7 % of which are formed of cubic metal nanoparticles) are composed of at least one metal selected from the group consisting of metals of Group VIII 299699.doc 1374119. The Group VIII metal is preferably selected from the group consisting of nickel, cobalt, iron, ruthenium, platinum, palladium and rhodium, very preferably selected from the group consisting of cobalt, nickel, platinum and palladium and more preferably from palladium. The metal nanoparticles prepared by the method of the present invention (at least 70 of which are formed of cubic metal nanoparticles) are advantageously composed of at least two metals, at least one of which is selected from the periodic table of the elements. Preferably, the Group VIII metal, the second metal is selected from the group consisting of Group VIII and Group IB metals of the Periodic Table of the Elements, very preferably selected from Group IB metals and more preferably selected from the group consisting of silver and gold.

各立方金屬奈米粒子可包含選自第VIII族金屬之單—金屬元素或若干種金屬元素，其中至少一者係選自第νπι族金屬；例如’其可為立方雙金屬奈米粒子，每一個係由第 VIII族金屬及第ΙΒ族金屬構成。較佳地，藉由本發明之方法獲得之該等金屬奈米粒子且尤其該等立方金屬奈米粒子為單金屬粒子且係由選自上文所給出之列舉的第νΠι族金屬、較佳為鈀構成。在包含複數個金屬元素之奈米粒子之情況下，此等金屬元素可以熟習此項技術者已知之任何方式組合。其可為任何混合物、合金、固體溶液或包含核心及殼之任何結構。詳言之，當該等奈米粒子為雙金屬粒子且係由纪及金或鈀及銀構成時，形成合金。該等使用本發明之方法製備之立方金屬奈米粒子具有在數埃至數百奈米之範圍内的邊長。較佳地，立方金屬奈米粒子之面之邊長在範圍2 nm至200 nm内，更佳地在範圍5 nm至1〇〇 nm内且更佳地在範圍$ nm至50 nmR。非常有利地，邊長係在範圍1 〇 nm至50 nm内，此係因為令人驚訝地 129699.doc -12· 1374119 顯示大於H) nm之邊長出乎意料地導致良好的催化效能。可使使用本發明之方法製備之金屬奈米粒子'尤其金屬奈米粒子相互分離或其可形成聚結物。其亦可藉接其之接觸點相互結合。一……弓丨入至少一種選自元素週期表第 VIII族金屬之金屬的至少一個來源來進行該製備方法之步Each cubic metal nanoparticle may comprise a single metal element selected from a metal of Group VIII or a plurality of metal elements, at least one of which is selected from the group consisting of a metal of the group νπι; for example, 'which may be a cubic bimetallic nanoparticle, each One consists of a Group VIII metal and a Group III metal. Preferably, the metal nanoparticles and especially the cubic metal nanoparticles obtained by the method of the present invention are single metal particles and are selected from the group of νΠι metal selected from the above, preferably. Made up of palladium. In the case of nanoparticles comprising a plurality of metal elements, such metal elements can be used in any combination known to those skilled in the art. It can be any mixture, alloy, solid solution or any structure comprising a core and a shell. In particular, when the nanoparticles are bimetallic particles and are composed of gold or palladium and silver, an alloy is formed. The cubic metal nanoparticles prepared by the method of the present invention have a side length in the range of several angstroms to several hundreds of nanometers. Preferably, the sides of the faces of the cubic metal nanoparticles are in the range of 2 nm to 200 nm, more preferably in the range of 5 nm to 1 〇〇 nm and more preferably in the range of $ nm to 50 nmR. Very advantageously, the side length is in the range of 1 〇 nm to 50 nm, which is surprisingly 129699.doc -12· 1374119 shows that the side length greater than H) nm unexpectedly leads to good catalytic performance. The metal nanoparticles prepared by the method of the present invention, especially metal nanoparticles, can be separated from each other or can form agglomerates. It can also be combined with each other by means of its contact points. Stepping into at least one source selected from the group consisting of metals of Group VIII metals of the Periodic Table of Elements to perform the preparation method

驟a)及進行步驟b),第VIII族金屬較佳係、選自錦/ 鐵釕-紅及銀，非常較佳地為選自録、錦、紐及免且更佳為其為鈀。為製備立方金屬奈米粒子，針對進行步驟a)引人之金屬與針料行該㈣bH丨人之㈣相同；^ 佳地’其為把。有利地，引入由選自第νιπ族金屬之單— 金^構成的單-來源來進行步驟a)接著進行步驟b)，從而獲仟金屬奈米粒子。更佳地，為根據本發明之方法製備立方金屬奈米粒+，引入鈀來源進行步驟a)接著5丨入鈀來源進行步驟b)。較佳地，為根據本發明之方法製備立方單金屬才、米粒子，針對進行本發明之方法之步驟a)所用的金屬來源與針對進行步驟b)所用的金屬來源相同。為製備立方雙金屬奈米粒子且在兩種金屬皆為第VIII族金屬之特殊情况下’必須引入兩種金屬之至少一者之至少—個來源來進订。玄步驟a)及進行該步驟b)。因此，可引人第—第族金屬之來源來進行步驟a)及/或步驟b)且可引入第二第¥111 族金屬之來源來進行步驟a)及/或步驟b)，其限制條件為存在兩個^源中之至少—者以進行該步驟a)及進行該步驟 b)。為製備立方雙金屬奈米粒子且在金屬之-者為第VIII 129699.doc 1374119 族金屬且另-金屬為第出族金屬（較佳選自金及銀）的特殊清況下可引入δ亥第IB族金屬之來源來進行步驟a)及/或步驟b)。用於進行本發明之方法之步叫叫的金屬來源之每一者可為考慮中之該金屬之前驅體的任何鹽，其對於該金屬具有大於0之氧化數且可溶於水性溶液中至少一種金屬係選自第vm族金屬。&鹽可為考慮中之金屬之鹵化物或氫氧化物’或齒化物及/或氮氧化物與驗金屬、胺基或氨結合而成之鹽。此鹽亦可為考慮中之金屬單獨地或與胺官能或氨相結合而形成之硝酸鹽、亞硝酸鹽或硫酸鹽。該金屬之該前驅體鹽亦可包含有機配位體；例如，其可為乙酸 Ιε。In the step a) and in the step b), the Group VIII metal is preferably selected from the group consisting of bromine/iron slag-red and silver, very preferably selected from the group consisting of bromine, brocade, and ruthenium, and more preferably palladium. In order to prepare the cubic metal nanoparticle, the metal and the needle material which are subjected to the step a) are the same as the (4) bH 丨 person (4); Advantageously, step a) is carried out by introducing a single-source consisting of a single-gold metal selected from the group consisting of a metal of the group νιπ, followed by step b), whereby the metal nanoparticles are obtained. More preferably, for the preparation of the cubic metal nanoparticles + according to the process of the invention, the introduction of the palladium source is carried out in step a) followed by 5 incorporation of the palladium source for step b). Preferably, the cubic single metal, rice particles are prepared according to the process of the invention, and the source of the metal used for carrying out step a) of the process of the invention is the same as the source of the metal used for carrying out step b). To prepare cubic bimetallic nanoparticles and to introduce at least one source of at least one of the two metals, in the special case where both metals are Group VIII metals. The step a) and the step b) are carried out. Thus, step a) and/or step b) can be carried out by introducing a source of the first-group metal and a source of the second group 111 metal can be introduced to carry out step a) and/or step b), the constraints In order to have at least one of the two sources, the step a) is carried out and the step b) is carried out. In order to prepare cubic bimetallic nanoparticles, and in the special condition of the metal which is the metal of the group VIII 129699.doc 1374119 and the other metal is the first group metal (preferably selected from gold and silver) The source of the Group IB metal is used to carry out step a) and/or step b). Each of the metal sources used to carry out the method of the present invention may be any salt of the metal precursor that is considered to have an oxidation number greater than zero for the metal and is soluble in the aqueous solution. One metal is selected from the group of vm metals. The & salt can be a salt of a metal halide or hydroxide or metallization and/or nitrogen oxide in combination with a metal, amine or ammonia. The salt may also be a nitrate, nitrite or sulfate formed by the metal under consideration either alone or in combination with an amine function or ammonia. The precursor salt of the metal may also comprise an organic ligand; for example, it may be acetic acid Ι ε.

當根據本發明製備包含鈀之立方金屬奈米粒子時，鈀來源可有利地為氯化鈀、溴化鈀、碘化鈀、六氯鈀酸鉀、六氣把義、四演―、四氣纪酸卸、四氯飽酸録、六氯鈀酸鈉、四氣鈀酸鈉、硝酸鈀、亞硝酸鈀、亞硝酸二胺纪、硫酸纪、硝酸四胺免、二氯二胺纪、乙酸飽或乙醯基丙酮鲅纪。較佳地，使用六氯鈀酸鉀、四氯鈀酸鉀、六氯纪酸鈉、四氣鈀酸鈉或硝酸鈀。當根據本發明製備包含鉑之立方金屬奈米粒子時，鉑來源可有利地為氯化鉑、#氣鉑酸鉀、六氯鉑酸銨、四溴鉑酸鉀、四氯鉑酸鉀、四氣鉑酸銨、六氯鉑酸鈉、四氯鉑酸納、硝酸细、亞硝酸#、亞硝酸二胺二翻' 硫酸翻 '硝酸四胺鉑、二氣二胺鉑 '乙酸鉑、乙醯基丙酮酸鉑、六氯鉑 I29699.doc •14· 1374119 酸、六羥基鉑酸、六溴鉑酸、氯化四胺鉑、六羥基鉑酸鉀或六經基純鈉。較佳地，使用六氯㈣鉀、四氯翻酸鉀、六氯鉑酸鈉、四氯鉑酸鈉或硝酸鉑。當根據本發明製備包含銀之立方金屬奈米粒子時，銀來源可有利地為乙酸銀、氯酸銀、高氣酸銀、硝酸銀、亞硝酸銀或硫酸銀。When preparing cubic metal nanoparticles comprising palladium according to the present invention, the palladium source may advantageously be palladium chloride, palladium bromide, palladium iodide, potassium hexachloropalladate, six gas, four, and four gases. Acid-depleted, tetrachloro-saturated acid, sodium hexachloropalladate, sodium tetrapentate, palladium nitrate, palladium nitrite, diamine nitrite, sulfate, tetraamine nitrate, dichlorodiamine, acetic acid Saturated or acetaminophen. Preferably, potassium hexachloropalladate, potassium tetrachloropalladate, sodium hexachlorochloride, sodium tetrapentate or palladium nitrate is used. When cubic metal nanoparticles comprising platinum are prepared in accordance with the present invention, the platinum source may advantageously be platinum chloride, potassium pentoxide, ammonium hexachloroplatinate, potassium tetrabromoplatinate, potassium tetrachloroplatinate, tetra Glycolate, sodium hexachloroplatinate, sodium tetrachloroplatinate, fine nitric acid, nitrous acid #, diamine nitrite, sulphate, sulphate, sulphate, sulphate, sulphate Platinylpyruvate, hexachloroplatin I29699.doc •14· 1374119 acid, hexahydroxyplatinic acid, hexabromoplatinic acid, tetraammineplatinum chloride, potassium hexahydroxyplatinate or pure sodium hexahydrate. Preferably, potassium hexachloro(tetra), potassium tetrachlorophosphate, sodium hexachloroplatinate, sodium tetrachloroplatinate or platinum nitrate is used. When cubic metal nanoparticles comprising silver are prepared in accordance with the present invention, the silver source may advantageously be silver acetate, silver chlorate, high acid silver, silver nitrate, silver nitrite or silver sulfate.

源金當根據本發明製備包含金之立方金屬奈米粒子時，金來可有利地為氣化金、硝酸金、硝金酸、氣金酸或乙酸用於進彳了本發明之方法之步驟a)及步驟b)的金屬、較佳二第in族金屬且更佳為紐之莫耳濃度在範圍！ X1 〇 $莫耳/ 么升至1莫耳/公升内，較佳地在範圍5x1 Ο·5莫耳/公升至 1X10莫耳/公升内，且更佳地在範圍lxlO-4莫耳/公升至 xiO莫耳/公升内。該莫耳濃度為存在於本發明之方法之步驟a)、步驟b)及步驟c)中所製備的水性溶液之每一者中之金屬的莫耳濃度。浐：據本發明，製備立方金屬奈米粒子之方法使用兩個連、貝還原步驟，第—個（步驟a))係使用還原劑R1進行且第二個步驟係使用化學組成不同於化合物R1之還原劑R2進 :丁根據本發明，化合物R2可引入在進行本發明之方法之 ^ v驟b)時所製備的水性溶液中或引入由混合步驟&)中獲 >之X丨生谷液與步驟b)中獲得之水性溶液所產生的溶液中有利地為將還原劑R2引入在進行本發明之方法之該步驟b)時所製備的水性溶液中。步驟卜）或。）之—者中存在還 129699.doc 1374119 原劑R2對本發明之方法中立方金屬奈米粒子的製備係必不可少的；不過，引入該化合物R2之時間選擇並不重要，只要化合物R2不與還原劑R1同時引入同一溶液中即可以便使兩個還原步驟連續進行。因此，該化合物们不能在進行本發明之方法之步驟a)時引入。 • 所使用之還原劑R1及R 2實質上可為無機物或有機物。較佳無機還原劑係選自氫、肼、羥胺、鹼金屬硼氫化物及氫化物。較佳有機還原劑係選自羧酸、醇、多元醇、醛、酮及其離子。更佳地，還原劑R1係選自由氫、肼、羥胺、鹼金屬硼氫化物及氫化物组成之群，且更佳地，Ri為化合物NaBh。更佳地，還原劑R2係選自由羧酸、醇、多元 • 醇、醛、酮及其離子組成之群。因此，對於還原劑R1有利 - 的為具有大於還原劑R2之還原能力。有利地，使用硼氫化鈉作為還原劑R1。有利地，使用羧酸根離子作為還原劑 R2。較佳地，在所利用之還原劑们具有質子化官能（諸如羧酸或醇）的情況下，較佳將鹼添加至含有呈質子化形式籲之該化合物R2之水性溶液中。更佳地，該驗為氮氧化納。添加鹼（較佳為氫氧化鈉）可藉由使質子化化合物R2去質子化而產生相應陰離子，該陰離子具有比質子化形式強的還原能力。較佳地，引入相對於呈質子化形式之還原劑^等莫耳之數量的鹼。有利地，R2為抗壞血酸或其去質子化形式，抗壞血酸鋼。在本發明之方法之步驟a)中所製備的水性溶液中還原劑 R1之莫耳濃度在範圍lxl0-5莫耳/公升至丨莫耳/公升内，較 129699.doc -16· ^74119Source Gold When preparing cubic metal nanoparticles comprising gold according to the present invention, gold may advantageously be used for gasification of gold, gold nitrate, nitonic acid, gas gold acid or acetic acid for the steps of the method of the invention. a) and the metal of step b), preferably the second indium metal and more preferably the concentration of the molar in the range! X1 〇$m / liter to 1 m / liter, preferably in the range 5x1 Ο · 5 m / liter to 1 x 10 m / liter, and more preferably in the range lxlO-4 m / liter To xiO Moere / liter. The molar concentration is the molar concentration of the metal present in each of the aqueous solutions prepared in steps a), b) and c) of the process of the invention.浐: According to the present invention, the method of preparing cubic metal nanoparticles uses two hydrazine and shell reduction steps, the first (step a)) is carried out using a reducing agent R1 and the second step is performed using a chemical composition different from the compound R1. Reducing agent R2: according to the invention, compound R2 can be introduced into the aqueous solution prepared by carrying out the process of the invention, or introduced into the mixing step & Preferably, the solution of the gluten solution and the aqueous solution obtained in step b) is introduced into the aqueous solution prepared by carrying out step b) of the process of the invention. Step Bu) or. The presence of 129699.doc 1374119 The agent R2 is essential for the preparation of cubic metal nanoparticles in the process of the invention; however, the timing of introduction of the compound R2 is not critical as long as the compound R2 is not The reducing agent R1 is simultaneously introduced into the same solution so that the two reduction steps are carried out continuously. Therefore, the compounds cannot be introduced at the step a) of the process of the present invention. • The reducing agents R1 and R 2 used may be substantially inorganic or organic. Preferred inorganic reducing agents are selected from the group consisting of hydrogen, hydrazine, hydroxylamine, alkali metal borohydrides and hydrides. Preferred organic reducing agents are selected from the group consisting of carboxylic acids, alcohols, polyols, aldehydes, ketones and their ions. More preferably, the reducing agent R1 is selected from the group consisting of hydrogen, hydrazine, hydroxylamine, alkali metal borohydride and hydride, and more preferably, Ri is the compound NaBh. More preferably, the reducing agent R2 is selected from the group consisting of carboxylic acids, alcohols, polyhydric alcohols, aldehydes, ketones and ions thereof. Therefore, it is advantageous for the reducing agent R1 to have a reducing ability greater than that of the reducing agent R2. Advantageously, sodium borohydride is used as reducing agent R1. Advantageously, carboxylate ions are used as reducing agent R2. Preferably, where the reducing agent utilized has a protonating function such as a carboxylic acid or an alcohol, it is preferred to add a base to the aqueous solution containing the compound R2 in protonated form. More preferably, the test is sodium oxynitride. The addition of a base, preferably sodium hydroxide, produces a corresponding anion by deprotonating the protonated compound R2, which has a greater reducing power than the protonated form. Preferably, a base is introduced in an amount relative to the amount of the reducing agent in the protonated form. Advantageously, R2 is ascorbic acid or its deprotonated form, ascorbic acid steel. The molar concentration of reducing agent R1 in the aqueous solution prepared in step a) of the process of the invention is in the range of lxl0-5 m/d to 丨mol/liter, compared to 129699.doc -16·^74119

佳地在範圍⑻Ο」莫耳/公升至】χ1〇·,莫耳/公升内，且更佳地在範圍㈣、耳/公升至⑻…耳/公相。較佳地，該/驟3)中所製備之水性溶液中該還原劑R1的莫耳漠度接近於該步I)中所製備之水性溶液中第彻族金屬的莫耳 j。該步驟a)中所製備之水性溶液中引人步驟a)的ri/金耳比率在範圍1至30内’較佳地在範圍⑴。内，且更 2在範圍山内。在本發明之方法之步驟b)^)中所製備的水性溶液中還原細之莫耳Μ在範圍1χ1().5莫耳/公升至1莫耳/公升内，較佳地在範圍5xl〇·5莫耳/公升至1χ1〇·ι 莫耳、/公升内，且更佳地在範圍1χ10·4莫耳/公升至1Χ10·2莫耳/公升内。較佳地，該步則）或步驟e)中所製備之水性溶，中"亥還原劑R2的莫耳濃度接近於該步驟b)或步驟中所製備之水性溶液中第V職金屬的莫耳濃度。步驟b)5iU) •備之水II溶液中引入步驟b)的R2/金屬莫耳比率視 U還原㈣之步驟而定在範圍α10内，較佳地在範圍i 至5内。根據本發明之方法，在穩定劑存在下進行步驟a)及b)。，用於進仃步驟&)及用於進行步驟b)之穩定劑較佳為界面活性劑或錯合劑。詩進行步驟b)之敎劑可具有與用於風―本發月方法之步驟a)之穩定劑相同的性質及相同的化予組成，或其可在其性質及/或化學組成方面不同。較佳地，面活性劑。明之方法之用於進行本發明之方法之至少一種穩定劑為界因此，使用至少一種界面活性劑作為進行本發步驟a)及/或步驟b)的穩定劑〇根據本發明，用 129699.doc 17 1374119 作穩定劑之界面活性劑為具有至少_個親水性極性官能及至少-個疏水性烴鏈之有機化合物^用作進行步驟a)之穩定劑t界面活性劑構成的水性溶液較佳&有莫耳濃度比由用於進行步驟a)之金屬來源構成之組合物高得多的該界面活性劑。根據由使用界面活性劑作為穩定劑來進行本發明之方法之步驟a)及/或步驟b)組成的本發明之實施例之一者該界面活性劑較佳為具有通式R(Rl)(R2)(R3)Xa，Yb之任何化合物，其中： • a&b採用值-2、-1 ' +1 或+2，其中 a+b=〇 ; • R為含有1至25個碳原子、較佳8至丨8個碳原子之烴鏈； R1、R2及R3為熟習此項技術者已知之任何脂族、芳族或雜芳族基團，R1、R2及R3可能相同或不同，較佳相同’且更佳地，Rl、R2及R3為甲基；The best is in the range (8) Ο "m / liter to χ 1 〇 ·, Moer / liter, and better in the range (four), ear / liter to (8) ... ear / public. Preferably, the molarity of the reducing agent R1 in the aqueous solution prepared in the step (3) is close to the molar amount of the thachal metal in the aqueous solution prepared in the step I). The ri/gold ratio of the step a) introduced in the aqueous solution prepared in the step a) is in the range of from 1 to 30, preferably in the range (1). Inside, and more 2 in the range of mountains. The reduced molybdenum in the aqueous solution prepared in step b) of the process of the invention is in the range of from 1 χ 1 (5. 5 m / liter to 1 m / liter, preferably in the range of 5 x 〇 • 5 m / liter to 1 χ 1 〇 · m Mo, / liter, and more preferably in the range of 1 χ 10 · 4 m / liter to 1 Χ 10 · 2 m / liter. Preferably, the molar concentration of the aqueous solution, the intermediate "Hai reductant R2 prepared in the step or the step e) is close to the V-position metal in the aqueous solution prepared in the step b) or the step Molar concentration. Step b) 5iU) • The R2/metal molar ratio introduced to step b) in the preparation of the water II solution is within the range α10, preferably in the range i to 5, depending on the step of U reduction (4). According to the process of the invention, steps a) and b) are carried out in the presence of a stabilizer. The stabilizer used in the step &) and the step b) are preferably surfactants or complexing agents. The tanning agent of step b) may have the same properties and the same chemical composition as the stabilizer used in step a) of the method of the present invention, or it may differ in its properties and/or chemical composition. Preferably, a surfactant. The at least one stabilizer for carrying out the process of the invention is defined by the method of the invention. Thus, at least one surfactant is used as a stabilizer for carrying out step a) and/or step b) of the present invention. According to the invention, 129,699.doc is used. 17 1374119 The surfactant as a stabilizer is an organic compound having at least one hydrophilic polar functional group and at least one hydrophobic hydrocarbon chain, and is preferably used as an aqueous solution for carrying out the stabilizer t surfactant of step a). There is a surfactant having a molar concentration that is much higher than the composition consisting of the metal source used to carry out step a). According to one of the embodiments of the present invention which comprises the step a) and/or the step b) of the method of the present invention by using a surfactant as a stabilizer, the surfactant preferably has the formula R(R1) ( R2) (R3) Any compound of Xa, Yb, wherein: • a&b takes the value -2, -1 '+1 or +2, where a+b=〇; • R is from 1 to 25 carbon atoms, Preferably, the hydrocarbon chain of 8 to 8 carbon atoms; R1, R2 and R3 are any aliphatic, aromatic or heteroaromatic groups known to those skilled in the art, and R1, R2 and R3 may be the same or different, Preferably, and preferably, Rl, R2 and R3 are methyl;

• X為選自由鹼金屬及鹼土金屬形成之群的元素或含有氮或硫之基團；較佳地，X為陽離子四級銨型元素； • γ為諸如鹵化物、硝酸鹽、亞硝酸鹽或硫酸鹽之陰離子元素或諸如驗金屬或驗土金屬之陽離子元素；較佳地’ Y為陰離子元素且非常較佳地為齒化物。較佳地，用於進行步驟a)及/或步驟b)之界面活性劑為鹵化四級銨鹽，尤其具有式H3C(CH2)n(CH3)3N+，Br·或 (CH3(CH2)n)4N+，Br·之鹽’ η在範圍1至1 5内。非常較佳地，該界面活性劑為具有式之溴化 129699.doc 18 1374119 六烷基三甲基銨（CTAB)。更有利地，界面活性劑為具有式HjCCCHiOuOSChNa之十二烷基硫酸鈉（SDS)、具有式 H3C(CH2)nS〇3Na之十二烷基磺酸鈉或具有式 H3C(CH2)iiC6H4S03Na之十二院基苯項酸鈉。在使用界面活性劑作為穩定劑來進行步驟幻及/或步驟b) 之情況下，有可能另外使用不同於已使用之界面活性劑但不過選自具有與上文所述相同之通式之化合物的共界面活性劑。• X is an element selected from the group consisting of alkali metals and alkaline earth metals or a group containing nitrogen or sulfur; preferably, X is a cationic quaternary ammonium type element; • γ is such as a halide, a nitrate, a nitrite Or an anion element of a sulphate or a cation element such as a metal or soil metal; preferably 'Y is an anion element and very preferably a dentate. Preferably, the surfactant used to carry out step a) and/or step b) is a halogenated quaternary ammonium salt, especially having the formula H3C(CH2)n(CH3)3N+, Br· or (CH3(CH2)n) 4N+, the salt of Br·'η is in the range of 1 to 15. Very preferably, the surfactant is of the formula bromine 129699.doc 18 1374119 hexaalkyltrimethylammonium (CTAB). More advantageously, the surfactant is sodium dodecyl sulfate (SDS) having the formula HjCCCHiOuOSChNa, sodium dodecylsulfonate having the formula H3C(CH2)nS〇3Na or twelve having the formula H3C(CH2)iiC6H4S03Na Hospital based sodium benzoate. In the case where a surfactant is used as a stabilizer to carry out the step and/or step b), it is possible to additionally use a surfactant different from the surfactant which has been used but is not selected from the same formula as described above. a common surfactant.

根據由利用錯合劑作為穩定劑來進行本發明之方法之步驟a)及/或步驟b)組成的本發明之另一實施例’有利地使用下列各物： •具有㈣官能之任何有機化合物，例如包含捧樣酸鹽、乙酸鹽或乙醯基丙酮酸鹽基團之任何化合物、諸如聚乙烯°比°各咬酮或聚丙稀酸納之聚合物、脂肪酸及/ 或羧酸（諸如油酸）或羥基酸；According to another embodiment of the invention consisting of step a) and/or step b) of the process of the invention using a complexing agent as a stabilizer, the following materials are advantageously used: • any organic compound having a (four) function, For example, any compound comprising a sulphate, acetate or acetal pyruvate group, a polymer such as a polyethylene ratio of each ketone or sodium polyacrylate, a fatty acid and/or a carboxylic acid (such as oleic acid) Or hydroxy acid;

•具有尚氯酸酯官能之任何有機化合物； • 具有胺官能機化合物；較佳脂族胺（諸如十六烷基胺）之任何有具有膦官能（例如三苯基膦或醋官能之任何有機化合物；三辛基膦氧化物）或膦酸例如辛烷硫醇或十具有硫醇官能之任何有機化合物二烷硫醇；具有硫酚以及 —亞磷酸酯或醇官能之任何有機化合物 129699.doc •19- 1374119 • 結合上文所列之若干官能的任何其它組合β 較佳地，用於進行該步驟幻及該步驟b)之穩定劑具有相同化學組成；其較佳為界面活性劑且更佳為具有式 (CHJdCH^N'Br·之溴化十六烷基三甲基銨（CTAB)。• any organic compound having a chlorate function; • having an amine functional organic compound; preferably any aliphatic amine such as hexadecylamine having any organic having a phosphine function (eg, triphenylphosphine or vinegar functionality) a compound; a trioctylphosphine oxide) or a phosphonic acid such as an octanethiol or any organic compound dialkylthiol having a thiol function; any organic compound having a thiophenol and a phosphite or an alcohol function 129699.doc • 19-1374119 • any other combination of several of the above-listed functionalities β. Preferably, the stabilizing agent used to carry out the step of step b) has the same chemical composition; it is preferably a surfactant and more Preferably, it has the formula (CHJdCH^N'Br· cetyltrimethylammonium bromide (CTAB).

本發明之方法之步驟a)中所製備的水性溶液中穩定劑之莫耳濃度在範圍0.01莫耳/公升至〇75莫耳/公升内，較佳地在範圍0.05莫耳/公升至〇5莫耳/公升内。本發明之方法之步驟b)中所製備的水性溶液中穩定劑之莫耳濃度在範圍 0.05莫耳/公升至i莫耳/公升内，較佳地在範圍〇」莫耳/公升至0.5莫耳/公升内。由用於進行步驟a)之穩定劑構成的水性溶液較佳具有莫耳濃度比由用於進行步驟幻之金屬來源構成之溶液所呈現高得多的該穩定劑。The molar concentration of the stabilizer in the aqueous solution prepared in step a) of the process of the invention ranges from 0.01 mol/liter to 〇75 mol/liter, preferably in the range 0.05 mol/liter to 〇5. Moor / liter inside. The molar concentration of the stabilizer in the aqueous solution prepared in step b) of the process of the invention ranges from 0.05 moles per liter to i moles per liter, preferably in the range 〇"m / liter to 0.5 mole Ear/litre. The aqueous solution consisting of the stabilizer used to carry out step a) preferably has a stabilizer having a much higher molar concentration than that exhibited by the solution used to carry out the step metal source.

根據本發明之方法之步驟a),製備至少一種含有至少一種選自第VIII族金屬之金屬的至少一個來源、至少一種還原劑R1及至少一種穩定劑的水性溶液。用於進行該步驟a)之第VIII族金屬、還原劑似及穩定劑係選自本說明書中以上所列之相應金屬、還原劑及穩定劑。較佳地，用於該步驟a)之金屬為鈀。較佳還原劑Ri為硼氫化鈉NaBH4。較佳穩定劑為具有式h3C_ (CH2)丨5(CH3)3N+，Br.之溴化十六烷基三甲基銨（CTAB)。在該步驟a)結束時獲得之水性溶液係藉由於在範圍2〇艺至40 C内之溫度下溶解至少一種第VIII族金屬之至少一個來源、至少一種穩定劑及至少一種還原劑R1來製備。還原 129699.doc -20· 劑R1較佳係在攪拌下添加❶將用於進行該步驟幻之穩定劑 (較佳係界面活性劑）維持於在範圍2〇〇c至4(rc内之溫度下，同時進行該步驟a)之過程中的還原步驟，以避免該穩定劑之結晶。該步驟約持續5分鐘至24小時。在本發明之方法之該步驟a)結束時獲得的水性溶液中，當穩定劑為界面活性劑時，界面活性劑/金屬莫耳比率係在範圍1至1000内，較佳地在範圍5〇至5〇〇内且更佳地在範圍100至400内。當穩定劑為錯合劑時，本發明之方法之步驟a)結束時獲得的水性溶液中之錯合劑/金屬莫耳比率係在範圍1至1000内，較佳地在範圍1〇〇至5〇〇内。該步驟勾中所製備之水性溶液中引入步驟a)的R1/金屬莫耳比率係在範圍1至30内，較佳地在範圍1至1〇内，且更佳地在範圍ι 至5内。在本發明之方法之步驟b)中，於嚴格大於7〇t>c且小於或等於啊之溫度下製備至少一種含有至少一種選自元素週期表第VIII族金屬之金屬之至少一個來源及至少一種穩定劑的水性溶液。用於進行該步驟b)之第VI„族金屬、穩定劑及（視情況）還原劑R2係選自呈現於本說明書中以上所述之相應列舉中的金屬、還原劑及穩定劑。較佳地，用於該步驟b)之金屬為把。較佳還原劑R2為抗壞血酸鈉。較佳穩定劑為具有式之漠化十六烧基三甲基銨 (CTAB) 〇為製備單金屬奈米粒子’用於進行該步驟b)之第㈣族 129699.doc 1374119 金屬係與用於進行該步驟a)之金屬相同；其較佳為纪。較佳地，用於進行步驟6)之金屬來源係與用於進行本發明之方法之步驟a)的金屬來源相同。為製備由第VIII族金屬及第族金屬構成之雙金屬奈米粒子，第把族金屬來源可在該步驟b)期^丨人；此—第m族金屬來源可能在本發明之方法之步称a)期間引入或可能不在本發明t方法之步驟^ 期間引入。用於進行本發明之方法之該步驟b)的穩定劑係、選自本說明書令以上所列之界面活性劑及錯合劑。較佳地，其為 CTAB。見It況用於進行本發明之方法之該步驟b)的還原劑係選自本說明書中以上所列之化合物。較佳地，其為抗壞血酸鈉。在步驟b)結束時獲得之水性溶液係藉由於嚴格高於贼且小於或等於80°c之溫度下溶解第vm族金屬之至少一個來源至夕一種穩定劑及（視情況）至少一種還原劑R2來製備田引入還原劑R2以進行本發明之方法之該步驟b)時，在引入該第VIII族金屬&源及該穩定劑後將其引入溶液中’ R2較佳係在攪拌下引入。步驟聊續丄分鐘至2小時。〆在本發明之方法之該步驟b)結束時獲得的水性溶液中，當穩定劑為界面活性劑時，4面活性劑，金屬莫耳比率在圍5至5G0内，較佳地在範圍5()至謂内且更佳地在範圍 50至1 〇〇内。當穩定劑為錯合劑時，進行本發明之方法之步驟b)、’Ό束時所獲得的水性溶液中之錯合劑/金屬莫耳比率 129699.doc •22· 1374119 在範圍1至5〇〇内，較佳地在範圍1〇〇至4〇〇内。在引入還原似2以進行步驟b)之情況下步驟b)中所製備之水性溶液中引入步驟b)的R2/金屬莫耳比率在範圍ljLi()内較佳地在範圍1至5内。根據本發明.，本發明之方法之該步驟b)必須於嚴格高於 70 C且小於或等於8〇。〇之溫度下進行。根據本發明之方法之步驟e)，將在該步驟a)結束時獲得According to step a) of the process of the invention, at least one aqueous solution comprising at least one source selected from the group consisting of metals of Group VIII metals, at least one reducing agent R1 and at least one stabilizer is prepared. The Group VIII metal, reducing agent and stabilizer used to carry out this step a) are selected from the corresponding metals, reducing agents and stabilizers listed above in this specification. Preferably, the metal used in this step a) is palladium. A preferred reducing agent Ri is sodium borohydride NaBH4. A preferred stabilizer is cetyltrimethylammonium bromide (CTAB) having the formula h3C_(CH2)丨5(CH3)3N+, Br. The aqueous solution obtained at the end of step a) is prepared by dissolving at least one source of at least one Group VIII metal, at least one stabilizer, and at least one reducing agent R1 at a temperature ranging from 2 to 40 C. . Reduction 129699.doc -20. The agent R1 is preferably added under stirring. The stabilizer used to carry out the step is preferably maintained at a temperature in the range of 2 〇〇c to 4 (rrc). The reduction step during the step a) is carried out simultaneously to avoid crystallization of the stabilizer. This step lasts about 5 minutes to 24 hours. In the aqueous solution obtained at the end of this step a) of the process of the invention, when the stabilizer is a surfactant, the surfactant/metal molar ratio is in the range of from 1 to 1000, preferably in the range of 5 〇. Within 5 且 and more preferably in the range of 100 to 400. When the stabilizer is a complexing agent, the ratio of the complexing agent/metal molar in the aqueous solution obtained at the end of step a) of the process of the invention is in the range of from 1 to 1000, preferably in the range of from 1 to 5 Torr. Inside. The R1/metal molar ratio introduced into step a) in the aqueous solution prepared in this step is in the range of 1 to 30, preferably in the range of 1 to 1 Torr, and more preferably in the range ι to 5 . In step b) of the process of the invention, at least one source comprising at least one metal selected from the group VIII metal of the Periodic Table of the Elements and at least at a temperature strictly greater than 7 〇t > c and less than or equal to An aqueous solution of a stabilizer. The Group VI metal, stabilizer, and (as appropriate) reducing agent R2 used to carry out the step b) are selected from the group consisting of metals, reducing agents and stabilizers presented in the above-listed examples of the present specification. Preferably, the metal used in the step b) is a preferred reducing agent R2 is sodium ascorbate. The preferred stabilizer is a desertified hexadecyltrimethylammonium (CTAB) having the formula: The particle 'for the step b) of the group (4) 129699.doc 1374119 metal is the same as the metal used to carry out the step a); preferably it is preferably a metal source for carrying out step 6) Is the same as the source of the metal used in the step a) of the method of the invention. To prepare the bimetallic nanoparticles composed of the Group VIII metal and the Group III metal, the source of the Group III metal can be in the step b) The source of the mth metal may be introduced during the step a) of the method of the invention or may not be introduced during the step of the method of the invention. Stabilization of the step b) for carrying out the method of the invention a surfactant selected from the above listed surfactants And a complexing agent. Preferably, it is CTAB. The reducing agent used in the step b) for carrying out the method of the present invention is selected from the compounds listed above in the specification. Preferably, it is sodium ascorbate. The aqueous solution obtained at the end of step b) is obtained by dissolving at least one source of the vm group metal at a temperature strictly higher than the thief and less than or equal to 80 ° C, and at least one reduction (as appropriate) When the agent R2 is used to prepare the field to introduce the reducing agent R2 to carry out the step b) of the method of the invention, the group VIII metal & source and the stabilizer are introduced into the solution after the introduction of the stabilizer. Introduced. The procedure is continued for a few minutes to 2 hours. 〆 In the aqueous solution obtained at the end of this step b) of the method of the present invention, when the stabilizer is a surfactant, the 4-sided active agent, the metal molar ratio is 5 to 5 G0, preferably in the range of 5 () to within the range and more preferably in the range of 50 to 1 。. When the stabilizer is a complexing agent, the steps b), 'Ό The wrong agent/metal molar ratio in the aqueous solution obtained at the time Rate 129699.doc • 22· 1374119 in the range 1 to 5 Torr, preferably in the range 1 〇〇 to 4 。. Prepared in step b) with the introduction of reduction 2 to carry out step b) The R2/metal molar ratio introduced into step b) in the aqueous solution is preferably in the range 1 to 5 in the range ljLi(). According to the invention, this step b) of the method of the invention must be strictly higher than 70 C and less than or equal to 8 Torr. The temperature is carried out at a temperature of 〇. Step e) of the method according to the invention will be obtained at the end of step a)

之该水性溶液的至少-部分與在該步驟_束時獲得之該水性溶液混合。根據該步驟c)於與進行本發明之方法之^ 齡)相同的溫度下將兩種溶液混合。步叫之持續時間二範圍1分鐘至72小時内。更硿_ w 旰内更確切而言’為製備具有〇.78之形L因子F的立方金屬奈米粒子， )捋續時間範圍為1 小時’而當金屬奈米粒子係以截頂立方體之形式 ^延長持續時間且通常在範圍1()小時至”小時内。當還原劑R2尚未引入在本發月製備的水性溶液中時，在二Γ 該步驟b)期間所及bw/t °合來自本發明之方法之步驟a) 冷文之別或之後引入該化合物们以進行該步驟小較佳地’在步驟〇期間’添加鹽以控制弓丨入疋劑與正形成之太半+ ; )孝心風之不未Μ之間的相類型之無機化m A 為任何之鹵化物陰離子，弋诂缺抽亂1匕物 .或硝酸鹽、亞硝酸鹽或硫酸鹽。較佳地，步驟c)中所添加 Λζ 係選自由鹼金屬及鹼土金屈鹵化物組成之群。並機金屬 Ο之溶液之總體積1〇-4莫、·止步驟莫耳的乾圍β，較佳地在 129699.doc •23· 丄少/4119 每公升經歷步驟C)之溶液之總體積5 x丨〇·4莫耳至〇.丨莫耳的範圍内，更佳地在每公升經歷步驟幻之溶液之總體積1χ1〇-3 莫耳至0.05莫耳的範圍内。根據步驟c)自在該步驟勾結束時獲得之水性溶液移除且與在該步驟b)結束時獲得之水性溶液混合的溶液之量使得還原成〇氧化數、源自該步驟a)中所製備之溶液且引入在該步驟b)結束時獲得之該水性溶液中的第Yu〗族金屬（較佳At least a portion of the aqueous solution is mixed with the aqueous solution obtained at the time of the step. The two solutions are mixed according to this step c) at the same temperature as the age at which the method of the invention is carried out. The duration of the step is 2 minutes from 1 minute to 72 hours. More 硿 w w 更更 ' 为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为Form ^ extended duration and usually in the range of 1 () hours to "hours." When the reducing agent R2 has not been introduced into the aqueous solution prepared in this month, the bw/t ° during the step b) Step a) from the method of the invention a) cold or a later introduction of the compound to carry out the step, preferably 'additional salt' during the step 以 to control the bowing of the sputum into the sputum and the formation of the halving + +; The inorganic type m A of the phase type between filial piety and wind is any halide anion, lacking 1 substance, or nitrate, nitrite or sulfate. Preferably, step c The lanthanum added is selected from the group consisting of alkali metal and alkaline earth gold quinone halides. The total volume of the solution of the parallel metal ruthenium is 1 〇 4 莫, and the dry circumference β of the step mole is preferably 129699. .doc •23· Reduced/4119 The total volume of solution per liter of step C) 5 x丨〇·4 Within the range of the ear to the 〇. 丨耳 ear, preferably in the range of 1 χ 1 〇 -3 摩尔 to 0.05 摩尔 per liter of the step solution of the phantom solution. According to the step c) obtained at the end of the step The amount of the aqueous solution removed and mixed with the aqueous solution obtained at the end of step b) is reduced to the oxime oxidation number, from the solution prepared in step a) and introduced at the end of step b) The obtained Yu group metal in the aqueous solution (preferably

為鈀）之濃度在範圍15.0X10·9莫耳/公升至16 〇χ1〇·6莫耳/公升内，較佳地在範圍31.0><1〇·8莫耳/公升至65χΐ〇_7莫耳/公升内。在ν驟a)中獲得之水性溶液之至少一部分與步驟匕）中獲得之水性溶液的混合物中，相對於針對進行該步驟b)引入之金屬量定義之金屬的濃度在範圍lxlO·5莫耳/公升至丨莫耳/公升内，較佳地在範圍5xl〇-5莫耳/公升至ΐχΐ(Γΐ莫耳; 公升内，且更佳地在範圍1χ1〇.4莫耳/公升至卜1〇_2莫耳/公The concentration of palladium) is in the range of 15.0 X 10 · 9 m / liter to 16 〇χ 1 〇 6 m / liter, preferably in the range of 31.0>< 1 〇 · 8 m / liter to 65 χΐ〇 7 m / liter. In the mixture of at least a portion of the aqueous solution obtained in ν a) and the aqueous solution obtained in step 匕), the concentration of the metal defined relative to the amount of metal introduced for carrying out the step b) is in the range of lxlO·5 mol / liter to 丨耳 / liter, preferably in the range of 5xl 〇 -5 m / liter to ΐχΐ (Γΐ莫耳; liters, and more preferably in the range of 1χ1〇.4m / liter to Bu 1 〇_2莫耳/公

升内；經定義為引入步驟b)中之穩定劑之量之比率的穩定劑之漠度在範圍G.G5莫耳/公升至丨莫耳/公升内，較佳地在範圍0.1莫耳/公升至G 5莫耳/公升内；還原劑R2之濃度在 :圍1 10莫耳/公升至i莫耳/公升内，較佳地在範圍5叫〇5 莫耳/公升至^0·，莫耳/公升内且更佳地在範圍⑻。·4莫耳/ 公升至lxlO-2莫耳/公升内。之ίΤ:明之方法之該步驟C)結束時’獲得於水性溶液中之金屬奈米粒子懸浮液。所形成之金屬奈米粒子全。f5數量的至少70數目。/。、較 129699.doc -24- 1374119 佳至少73數目％具有立方形態。在進行本發明之製備方法時獲得之立方金屬奈米粒子具有在範圍〇 78至〇 81内之形態因子。不呈立方形態之金屬奈米粒子具有不在範圍〇78 至0.81内之形態因子且不超過所形成之金屬奈米粒子之全部數量的3 G數目％。立方金屬奈米粒子之比例係藉由對所形成之所有奈米粒子統計計數來測定且藉由如本說明書中以上所述之透射電予顯微術來檢視。The insufficiency of the stabilizer defined as the ratio of the amount of stabilizer introduced in step b) is in the range of G.G5 mol/liter to 丨mol/liter, preferably in the range of 0.1 mol/ Liters up to G 5 m / liter; the concentration of reducing agent R2 is in the range of 10 10 m / liter to i m / liter, preferably in the range 5 is 〇 5 m / liter to ^ 0 ·, Mohr/litre and better in range (8). · 4 m / liter to lxlO-2 m / liter. The metal nanoparticle suspension obtained in the aqueous solution at the end of this step C) of the method of Ming. The formed metal nanoparticles are all. At least 70 of the number of f5. /. Compared with 129699.doc -24-1374119, at least 73% of the population has a cubic form. The cubic metal nanoparticles obtained in carrying out the production method of the present invention have a shape factor in the range of 〇 78 to 〇 81. The metal nanoparticles which are not in a cubic form have a form factor which is not in the range of 〇78 to 0.81 and does not exceed the total number of 3 G% of the formed metal nanoparticles. The ratio of cubic metal nanoparticles is determined by statistically counting all of the nanoparticles formed and is examined by transmission electron microscopy as described above in this specification.

接著在本發明之方法之步驟d)中使至少7〇數目％呈立方形態且在該步驟c)結束時獲得之金屬奈米粒子沈積於載體上0 用於進行該步驟d)之載體較佳係基於至少一種選自氧化鋁、二氧化石夕、二氧化石夕-氧化銘、氧化鎂、氧化錯、氧 • 化妇^、二氧化欽之而才火氧化物，其呈單獨者或混合物形式。較佳地，該載體為氧化鋁、二氧化矽或二氧化矽-氧化鋁《該載體亦可為煤、矽鋁酸鹽、黏土或已知可用作如 ··本發明所定義之載體的任何其他化合物。該載體有利地具有在範圍5 m/g至300 m/g内之BET比表面積。其可以粉末之形式使用，或其可形成為珠粒、擠出物、三葉狀物、粉 ‘末或單石。使至少70數目。/。呈立方形態之該等金屬奈米粒子沈積於載體表面上係使用熟習此項技術者已知之任何方式進行，有利地藉由乾式浸潰來進行。較佳地，將在該㈣e)期間形成之金屬奈米粒子濃縮於液體中，使用熟習此項技術者已知之任何方式使其以懸浮 129699.doc -25- 1374119 液形式含於該液體t。有利地藉由於在範圍1〇〇〇至6〇〇〇 rpm内之速度下進行的離心來將其濃縮歷時在範圍15分鐘至1小時内之時間，例如於5000 rpm下歷時45分鐘。接著，抽ώ所形成之基本上且較佳完全不含奈米粒子之上清液。接著使經濃縮之溶液乾式浸潰於載體上：於周圍溫度下藉由逐滴添加緩慢地使溶液接觸載體。藉由攪拌使溶液-載體混合物均質化。接著於在範圍内較Next, in step d) of the method of the invention, at least 7 % of the number of cubes are in a cubic form and the metal nanoparticles obtained at the end of the step c) are deposited on the support. Preferably, the support for carrying out the step d) is preferably carried out. Based on at least one selected from the group consisting of alumina, sulphur dioxide, sulphur dioxide, sulphur oxide, oxidized oxidized, oxygenated, oxidized, and oxidized oxides, which are individual or mixture form. Preferably, the support is alumina, ceria or cerium oxide-alumina. The support may also be coal, yttrium aluminate, clay or a carrier known to be useful as a carrier as defined in the present invention. Any other compound. The support advantageously has a BET specific surface area in the range of 5 m/g to 300 m/g. It may be used in the form of a powder, or it may be formed into beads, extrudates, trilobes, powders or monoliths. Make at least 70 numbers. /. The deposition of the metal nanoparticles in a cubic form on the surface of the support is carried out by any means known to those skilled in the art, advantageously by dry impregnation. Preferably, the metal nanoparticles formed during the (d) e) are concentrated in a liquid and are included in the liquid t in the form of a suspension 129699.doc -25-1374119 in any manner known to those skilled in the art. It is advantageously concentrated by centrifugation over a range of 1 Torr to 6 rpm for a period of time ranging from 15 minutes to 1 hour, for example 45 minutes at 5000 rpm. Subsequently, the convulsions are formed substantially and preferably completely free of supernatant from the nanoparticles. The concentrated solution is then dry impregnated onto the support: the solution is slowly contacted with the support by dropwise addition at ambient temperature. The solution-carrier mixture was homogenized by stirring. Then in the range

佳在範圍20t至50°C内之溫度下將該等金屬奈米粒子之經浸漬載體乾燥，歷時在範圍6小時至24小時内、較佳在範圍10小時至15小時内之時間。根據本發明’方法執行兩個不同還原步驟。當在本發明之方法之步驟a)期間使至少一種選自第彻族金屬之金屬之來源接觸還原劑R1時，進行第一還原步驟。在使用該還原細還原該至少一種第彻族金屬之來源後，此第一步 =致產生奈米粒子晶種’其並不具有適當確定之形態且不具有立方形態。此第一還原步驟被有利地稱為接於η =等奈米粒子晶種為於水性溶液令之懸浮液。用等曰：二Γ)之穩定劑可藉由防止形成聚結物而維持該之：等二Γ呈充分分散形式。當將在步輝a)期間製備 …:種加入源自本發明之方法之步驟b)的溶第-#历丰，’在本毛明之方法之該步驟Ο期間進行 :一還原步驟。在通常稱為生長步驟之該第二還原步驟中，形成未經負裁之太丰决使用該還原歌2還^ 驟）中之至少-種金屬來源後且在步叫中製備之晶 I29699.doc -26- 1374119 種存在下，藉由該等晶種之生長而形成具有立方形態之金屬奈米粒子。.另外，該第二還原步驟有利地適於作為生長步驟。引人本發明之方法之該步則）中的穩定劑藉由根據本發明之方法之該步驟^且於上文給出之溫度條件（亦即嚴格大於m：且小於或等於_之溫度)下促使呈立方形態之奈米粒子晶種受控生長而充當選擇性生長試劑。Preferably, the metal nanoparticles are impregnated with the impregnated support at a temperature in the range of from 20 t to 50 ° C for a period of from 6 hours to 24 hours, preferably from 10 hours to 15 hours. Two different reduction steps are performed in accordance with the present invention. The first reduction step is carried out when at least one source selected from the group consisting of metals of the Group 13 metal is contacted with the reducing agent R1 during step a) of the process of the invention. After the reduction is used to reduce the source of the at least one of the Group III metals, this first step = results in the production of nanoparticle seed crystals which do not have a well-defined morphology and do not have a cubic morphology. This first reduction step is advantageously referred to as contacting the η = equal nanoparticle seed crystals as a suspension in an aqueous solution. Stabilizers can be maintained by preventing the formation of agglomerates: the diterpene is in a fully dispersed form. When it is prepared during step a), the addition of a solution derived from step b) of the process of the invention is carried out during the step 本 of the method of the present invention: a reduction step. In the second reduction step, which is generally referred to as the growth step, the formation of the crystal I29699 which is prepared in the step call is performed without using a negative cut. In the presence of doc -26- 1374119, metal nanoparticles having a cubic form are formed by the growth of the seed crystals. Additionally, the second reduction step is advantageously adapted as a growth step. The stabilizer in the step of the method of the invention is obtained by the step according to the method of the invention and the temperature conditions given above (ie, strictly greater than m: and less than or equal to _) The nanoparticle seed crystals in a cubic form are controlled to grow as a selective growth reagent.

洗蘇步驟e)較佳係在本發明之方法之該步驟d)後進行。該步驟e)由洗滌該等經負載金屬奈米粒子組成。其在乾燥經浸潰載體之步驟之前或之後進行。使該經奈求粒子浸潰之載體接觸水/醇混合物，較佳為水/乙醇。均質化後，過據洗務水。該操作有利地為再重複兩次。本發明亦係關於一種由根據本發明之方法製備之經負載立方金屬奈米粒子形成的催化劑。The washing step e) is preferably carried out after this step d) of the method of the invention. This step e) consists of washing the supported metal nanoparticles. It is carried out before or after the step of drying the impregnated carrier. The carrier impregnated with the particles is contacted with a water/alcohol mixture, preferably water/ethanol. After homogenization, the water is washed. This operation is advantageously repeated two more times. The invention also relates to a catalyst formed from supported cubic metal nanoparticles prepared by the process of the invention.

有利地，由該等經負載奈米粒子形成之該催化劑於還原氣氛中、於小於400°c或小於loot：或甚至小於8(rC45(rc 之溫度下經受活化處理。由該等經負載奈米粒子形成之該催化劑有利地為在其組成上包含一或多種元素，例如有利地選自鎵及銦之第IIIA 族元素；有利地選自鍺及錫之第IVA族元素；較佳為銅之第IB族元素；有利地選自經、鈉及卸之第丨八族元素；有利地選自鎮、鈣、鰓及鋇之第IIA族元素；及齒素β藉由浸潰包含金屬奈米粒子之載體將該等元素引入催化劑上。該等元素可在於上文所述之還原氣氛下活化處理之前或之後進行浸潰。 129699.doc -27· 1374119 當存在於催化組合物中時，第ΙΑ族及/或第IIA族元素之量在範圍〇·〇1重量％至20重量％内，較佳地在範圍0.01重量 %至10重量％内，更佳地在範圍001重量％至5重量％内。當至少一種齒素元素存在於催化組合物中時，該元素之量在範圍0.01重量％至〇.2重量％内。Advantageously, the catalyst formed from the supported nanoparticles is subjected to an activation treatment in a reducing atmosphere at a temperature of less than 400 ° C or less than a loot: or even less than 8 (rC45 (rc). The catalyst formed by the rice particles advantageously comprises one or more elements in its composition, for example a Group IIIA element advantageously selected from the group consisting of gallium and indium; a Group IVA element advantageously selected from the group consisting of antimony and tin; preferably copper a Group IB element; advantageously selected from the group consisting of sodium, sodium and unloaded elements of Group VIII; advantageously selected from Group IIA elements of towns, calcium, strontium and barium; and dentate β comprising metal naphthalene by impregnation The carrier of the rice particles introduces the elements onto the catalyst. The elements may be impregnated before or after the activation treatment under the reducing atmosphere described above. 129699.doc -27·1374119 When present in the catalytic composition, The amount of the Group III and/or Group IIA elements is in the range of from 1% by weight to 20% by weight, preferably from 0.01% by weight to 10% by weight, more preferably from 001% by weight to 5 parts by weight. Within % by weight. When at least one dentin element is present in the reminder The composition, the amount of the element in a range of 0.01 wt.% Wt.% To 〇.2.

存在於該催化劑中之第νιπ族金屬（有利地為鈀）之量較佳地在該催化劑之〇·〇 1重量。/。至20重量％的範圍内，較佳地在該催化劑之0.01重量％至1〇重量％的範圍内且更佳地在該催化劑之0·01重量％至1重量％的範圍内。第ΙΒ族金屬（當此類金屬存在於催化組合物中時）之量在該催化劑之0.01重量❾/〇至20重量％的範圍内，較佳地在該催化劑之0.01重量％至1〇重量％的範圍内且更佳地在該催化劑之0.01重量％至1重量％的範圍内。The amount of the metal of the νιπ group (preferably palladium) present in the catalyst is preferably at a weight of 催化剂·〇 of the catalyst. /. In the range of 20% by weight, preferably in the range of 0.01% by weight to 1% by weight of the catalyst and more preferably in the range of 0. 01% by weight to 1% by weight of the catalyst. The amount of the third metal (when such a metal is present in the catalytic composition) is in the range of from 0.01% by weight to 20% by weight of the catalyst, preferably from 0.01% by weight to 1% by weight of the catalyst. Within the range of % and more preferably in the range of from 0.01% by weight to 1% by weight of the catalyst.

更確切而言，將包含至少70數目。/。呈立方形態之該等金屬奈米粒子的催化劑用於有機分子之催化轉化，尤其用於不飽和烴（例如二烯烴或乙炔）之選擇性氫化。選擇性氫化通常意在使用鈀基催化劑純化來自蒸汽裂化器或來自催化裂化之排出物，如WK Lam，L Lloyd，Oil &More precisely, it will contain at least 70 numbers. /. Catalysts of such metal nanoparticles in cubic form are used for the catalytic conversion of organic molecules, especially for the selective hydrogenation of unsaturated hydrocarbons such as diolefins or acetylene. Selective hydrogenation is generally intended to purify effluents from steam crackers or from catalytic cracking using palladium based catalysts such as WK Lam, L Lloyd, Oil &

Gas Journal，第 66-70頁，1972年3月所述。可參考 ep_a_〇 899 012中所述之選擇性氫化二烯烴或乙炔之使用條件。通*用於進行使用基於立方金屬奈米粒子之催化劑之選擇性氫化過程的操作條件為在範圍丨5。〇至2〇(rc内之平均溫度、在範圍〇· 1 〇/0至10 MPa内之總壓力及在範圍1至丨5〇内之氫與烴的莫耳比率。 129699.doc • 28 · 1374119 實例八在下列實例中說明製造本發明之奈米粒子之方法。將包含直接藉由本發明之方法獲得之奈米粒子的催化劑之效能與藉由先前技術方法獲得之催化劑的效能進行比較。此等實例係作為*例而給出，而並不限制本發明之範嘴。用於此等實例之催化劑之奈米粒子的形態係、藉由透射電子顯微術表徵。所使用之透射電子顯微鏡為由㈣l出售之〇1 2010◎型號。此顯微鏡具有200 kv之加速張力、02 nm之空間解析率及大約〇 7咖之谓冑限度（針冑經負載金屬粒子而言）。使用由 Image Processing and Analysis, Princeton GammaGas Journal, pp. 66-70, March 1972. Reference may be made to the conditions of use of the selectively hydrogenated diolefin or acetylene described in ep_a_〇 899 012. The operating conditions for performing the selective hydrogenation process using a catalyst based on cubic metal nanoparticles are in the range of 丨5. 〇 to 2〇 (the average temperature in rc, the total pressure in the range 〇·1 〇/0 to 10 MPa and the molar ratio of hydrogen to hydrocarbon in the range 1 to 丨5〇. 129699.doc • 28 · 1374119 Example 8 A method of producing the nanoparticles of the present invention is illustrated in the following examples. The performance of a catalyst comprising nanoparticles directly obtained by the method of the present invention is compared with the performance of a catalyst obtained by the prior art method. The examples are given as * and do not limit the scope of the invention. The morphology of the nanoparticles used in the catalysts of these examples is characterized by transmission electron microscopy. It is sold by (4)l. The model has a speed of 200 kv, a spatial resolution of 02 nm, and a limit of about 咖7 coffee (in terms of supported metal particles). And Analysis, Princeton Gamma

Tech開發之IMAGISTC)影像處理軟體測定形態因子f。藉由直接於TEM影像上進行之統計計數測定立方金屬奈米粒子·對於代表藉由TEM分析之整個樣品的200個奈米粒子之奈米粒子群體而言，對立方奈米粒子之數目計數。在進行透射電子顯微術表徵之前，使用包括以下步驟之耘序製備催化劑樣品：溶解於乙醇中、使一滴溶液沈積於分析柵格上、乾燥該柵格及將該柵格引入顯微鏡中。實例1:主要為具有形態因子F=〇78之經負載鈀奈米粒子 (催化劑A，根據本發明）之合成。首先，將12.5 ml濃度為1〇·3莫耳/公升之K2PdCl4.3H20水溶液添加至25 ml濃度為0.15莫耳/公升之溴化十六烷基三甲基銨水溶液中。接著在攪拌下添加3 ml濃度為〇.〇丨莫耳/ 公升之硼氫化鈉水溶液。於3〇°C下攪拌1 〇分鐘後，使已製 129699.doc -29- 1374119The IMAGISTC) image processing software developed by Tech measures the form factor f. The cubic metal nanoparticles were determined by statistical counting directly on the TEM image. For the population of nanoparticles representing 200 nanoparticles of the entire sample by TEM analysis, the number of cubic nanoparticles was counted. Prior to performing transmission electron microscopy characterization, a catalyst sample was prepared using a procedure comprising the steps of dissolving in ethanol, depositing a drop of solution onto the analytical grid, drying the grid, and introducing the grid into the microscope. Example 1: Synthesis of mainly supported palladium nanoparticles (catalyst A, according to the invention) having a morphological factor F = 〇78. First, 12.5 ml of a K2PdCl4.3H20 aqueous solution having a concentration of 1 〇·3 mol/liter was added to 25 ml of an aqueous solution of cetyltrimethylammonium bromide having a concentration of 0.15 mol/liter. Then, 3 ml of an aqueous solution of sodium borohydride having a concentration of 〇.〇丨mol/liter was added under stirring. After stirring at 3 °C for 1 〇 minutes, make 129699.doc -29- 1374119

基三曱基錄之量的比率）W.U74 M ;抗壞血酸鈉還原劑之濃度為1.568M0-3 Μ，從而得到8〇〇3之漠化十六院基三備之奈米粒子晶種溶液a)靜置2小時。於溶液a)中尺2_4之濃度為3〇8χ1〇·4 M;溴化十六烷基三甲基銨之濃度為0.0925 M ;還原劑NaBH4之濃度為 M’從而得到则之演化十六院基三甲基舰2p^ 莫耳比率及2.4之NaBfVKJdCl4莫耳比率。其次，將_ d濃度為3xl0-3莫耳/公升之K2pda4為〇水溶液添加至於72t：下怪溫d〇〇ml〇24莫耳/公升漠化十六燒基三甲基錄水溶液中。5 _後，逐滴添加4mi濃度為 0.08莫耳/公升之抗壞▲酸納溶液。接著將鳩叫容液^添加至此溶液（稱為溶液b))中1由此形成之溶液〇搜掉ι〇 min ’接著於72亡下靜置3小時。於溶液b)tK2PdCl4之漠度~.47χ1〇·3 M;演化十六院基二甲基録之濃度為0.1176 M ;抗壞血酸鈉還原劑之濃度為1.568X103 Μ，亦即溴化十六烷基三甲基敍/K2pdc丨4莫耳比率為80 ’且抗壞金酸納/K2pdcl4莫耳比率^術。於溶液WK2Pdcl4之濃度（相對於在製備溶液b)期間引入之K2PdCl4量定義⑷467χ1〇·3 M;漠化十六炫基三甲基録之濃度（經定義為在製備溶液b)期間引人之漠化十六烧 f基敍/K2Pdci4莫耳比率及！ _之抗壞血酸納/κ心⑶莫耳比率”原自溶液a)且存在於溶液e)中之具有0氧化數的還原鈀之濃度為5.62X10·7莫耳/公升。所形成之奈米粒子係由75%立方體（形態因 129699.doc 子為0.78)、 -30- 1374119 10%棒狀物(形態因子<0·7)、15%多面體構成。所形成之奈米粒子主要具有0.78之形態因子。立方體具有對於邊所量測之3 0 nm之尺寸。在藉由離心減小溶液幻之體積後，藉由乾式浸潰使鈀奈米粒子沈積於氧化链上。接著經由布氏漏斗（Buchner funnel)，使用2xi〇〇 ml水/The ratio of the amount of the base of the base group) W.U74 M; the concentration of the sodium ascorbate reducing agent is 1.568M0-3 Μ, thereby obtaining the solution of 8〇〇3 of the desertification a) Allow to stand for 2 hours. The concentration of the ruler 2_4 in the solution a) is 3〇8χ1〇·4 M; the concentration of cetyltrimethylammonium bromide is 0.0925 M; the concentration of the reducing agent NaBH4 is M′, thereby obtaining the evolution of the 16th The base trimethyl 2p^ molar ratio and the 2.4 NaBfVKJdCl4 molar ratio. Next, K2pda4 with a concentration of _d of 3xl0-3 mol/L was added as an aqueous solution of hydrazine to 72t: a lower temperature d〇〇ml〇24mol/liter of desertified hexamethyl-trimethylamine aqueous solution. After 5 _, a 4 μ molar concentration of 0.08 mol/liter of anti-bad ▲ soda solution was added dropwise. Next, the squeaking solution was added to this solution (referred to as solution b)). 1 The solution thus formed was searched for ι min min' and then allowed to stand for 72 hours at 72 deaths. In solution b) the indifference of tK2PdCl4 ~.47χ1〇·3 M; the concentration of the hexamethylene dimethyl group recorded is 0.1176 M; the concentration of sodium ascorbate reducing agent is 1.568X103 Μ, ie cetyl bromide The trimethyls/K2pdc丨4 molar ratio is 80' and the anti-sodium chlorate/K2pdcl4 molar ratio is reduced. The concentration of K2PdCl4 introduced during the concentration of solution WK2Pdcl4 (relative to the preparation of solution b) is defined as (4) 467χ1〇·3 M; the concentration of desertification hexadecyltrimethyl group (defined as preparation solution b) is attractive. Desertification 16 burning f base / K2Pdci4 molar ratio and! _ of the ascorbate/κ (3) molar ratio "originally from solution a) and the concentration of reduced palladium having a zero oxidation number present in solution e) is 5.62 X 10.7 mol / liter. It consists of 75% cube (morphology factor 129699.doc is 0.78), -30-1374119 10% rod (morphological factor <0·7), 15% polyhedron. The formed nanoparticle mainly has 0.78 Morphological factor. The cube has a size of 30 nm measured for the edge. After reducing the volume of the solution by centrifugation, the palladium nanoparticles are deposited on the oxidized chain by dry impregnation. (Buchner funnel), using 2xi〇〇ml water/

乙醇混合物（20%水/80%乙醇）洗滌由該等經負載奈米粒子形成之催化劑。接著將催化劑於30°C下乾燥隔夜。如此製備之催化劑a 含有〇.3重量％鈀。tem相片展示於圖i中。實例2:主要具有形態因子F=〇78之經負載鈀奈米粒子(催化劑B，根據本發明）之合成。The ethanol mixture (20% water / 80% ethanol) was washed with the catalyst formed by the supported nanoparticles. The catalyst was then dried overnight at 30 °C. The catalyst a thus prepared contained 0.3% by weight of palladium. The tem photo is shown in Figure i. Example 2: Synthesis of supported palladium nanoparticles (catalyst B, according to the invention) having predominantly a morphological factor F = 〇78.

首先將12.5 濃度為1〇_3莫耳/公升之K2PdCl4.3H20水溶液添加至25 ml濃度為0.15莫耳/公升之溴化十六烷基三甲基敍水/合液中。接著在攪拌下添加3爪!濃度為莫耳/ 公升之硼氫化鈉水溶液。於3〇r下攪拌1〇分鐘後使已製備之奈米粒子晶種溶液a)靜置2小時。於溶液a)中K2PdCl4、漠化十六貌基三甲基錄及㈣仏之濃度與實例1中的濃度相同。溴化十六烷基三曱基銨/First, a 12.5 K2PdCl4.3H20 aqueous solution having a concentration of 1 〇 3 mol/L was added to 25 ml of a 0.15 mol/liter clonadecyltrimethyl sulphate/water mixture. Next, 3 claws were added with stirring to a molar concentration of liters of aqueous sodium borohydride solution. After stirring for 1 minute at 3 Torr, the prepared nanoparticle seed crystal solution a) was allowed to stand for 2 hours. The concentrations of K2PdCl4, desertified hexadecane trimethylate and (iv) hydrazine in solution a) were the same as those in Example 1. Cetyltrimethylammonium bromide /

KedCU及^叫似们4比率亦與實例丨之比率相同。其次，將100 ml濃度為3xl〇-3莫耳/公升之K2pdci43H2〇水溶液添加至於8(rc下恆溫之10〇1111〇24莫耳/公升漠化十六烧基三甲基财溶液15_後，逐滴添加4ml濃度為 0.08莫耳/公升之抗壞血酸鋼溶液。接著將则μΐ溶液a)添 129699.doc :至此溶液(稱為溶液b))t。將由此形成之溶液侧10 n ,接者於8〇t下靜置3小時。 4 b) t K2Pda4 n十六烧基三甲基敍及抗壞血 Λ之濃度與實例1中的濃度相同。漠化十六炫基三尹基叙/K2PcK：U抗壞血酸鈉/K2pda4莫耳比率亦與實例！之莫耳比率相同。、相對於在製備溶液b)期間引入之K2pdcl4及漠化十六院基三曱基錄之量表示的於溶液c^K2pdcl4、漠〖十六燒基三’基銨及抗壞血酸鈉之濃度與實例1之濃度相同。溴化十/、烷基—甲基銨/K^Pdcl4及抗壞血酸鈉/K2pdCi4莫耳比率亦與實例1之莫耳比率相同。源自溶液a)且存在於溶液〇) 中之具有0氧化數的還原鈀之濃度為5 62χ1〇·7莫耳/公升。所形成之奈米粒子係由74%立方體（形態因子為0 78)、 7〇/。棒狀物（形態因子<〇·7)、7%多面體及i 2%四面體構成。 TEM相片展示於圖2中。在藉由離心減小溶液为之體積後，藉由乾式浸潰使鈀奈米粒子沈積於氧化鋁上。接著經由布氏漏斗，使用2x 1〇〇 mi水/乙醇混合物（2〇0/〇水/80°/。乙醇）洗滌由該等經負載奈米粒子形成之催化劑。接著將催化劑於30°C下乾燥隔夜。如此製備之催化劑B 含有0.3重量％ Is。實例3:並非主要為具有形態因子F=〇78之經負載把奈米粒子（催化劑C，不根據本發明）之合成。首先’將12_5 ml濃度為1〇·3莫耳/公升之K2pdcl4.3H2〇水 129699.doc -32- 1374119 冷液添加至25 ml濃度為〇15莫耳/公升之溴化十六烷基三甲基敍水溶液中。接著在授拌下添加3 mU農度為0.01莫耳/ 么升之硼虱化鈉水溶液。於3〇。〇下攪拌1〇分鐘後使已製備之奈米粒子晶種溶液a)靜置2小時。 . 於溶液中、漠化十六烧基三甲基錢及NaBH4之 • 濃度與實例1中的濃度相同。演化十六烷基三甲基銨/ hPdCU及NaBH4/K2Pda4莫耳比率亦與實例丨之莫耳比率相同。 ^ miGG mUt 度為 3W3 莫很狀 K2PdCl4.3H2〇水溶液添加至於贼下值溫之1〇〇 ml 〇24莫耳/公升漠化十六炫基三曱基敍水溶液中。5 min後，逐滴添加4ml濃度為 0.08莫耳/公升之抗壞血酸鈉溶液。接著將36〇 y溶液勾添加至此溶液（稱為溶液b))f。將由此形成之溶液匀攪拌⑺ min，接著於5(TC下靜置3小時。於溶液b)中IPdC丨ρ填化十六烧基三甲基錢及抗壞灰 •# 酸鈉之濃度與實例1中的濃度相同。溴化十六烷基三曱基銨/KJdCl4及抗壞血酸鈉/K2Pdcl4莫耳比率亦與實例^之莫耳比率相同β 相對於在製備溶液b)期間引入之KJdCl4及溴化十六烷基三甲基銨之量表示的於溶液c)+K2Pdcl4、溴化十六烷基三甲基銨及抗壞血酸鈉之濃度與實例i之濃度相同。溴化十六烷基三甲基銨/KJdCl4及抗壞血酸鈉/K2Pdcl4莫耳比率亦與實例1之莫耳比率相同。源自溶液a)且存在於溶液C) 中之具有0氧化數的還原鈀之濃度為5 62xl0-7莫耳/公升。 129699.doc •33· 1374119 所形成之奈米粒子係由58%立方體（形態因子為0·78)、 1 1%棒狀物（形態因子< 0.7)、10%多面體及21%四面體構成。在藉由離心減小溶液匀之體積後，藉由乾式浸潰使鈀奈米粒子沈積於氧化鋁上。接者經由布氏漏斗，使用2 X 1 〇〇 mi水/乙醇混合物（2〇〇/0 水/80%乙醇）洗滌由該等經負載奈米粒子形成之催化劑。The KedCU and ^likes 4 ratios are also the same as the ratios of the examples. Next, add 100 ml of a concentration of 3xl〇-3 mol/L of K2pdci43H2 〇 aqueous solution to 8 (after 10 rc under constant temperature of 10 〇 1111 〇 24 mol / liter of desertified hexadecyl trimethyl ketone solution 15_ 4 ml of a 0.08 mol/liter ascorbic acid steel solution was added dropwise. Then, the μΐ solution a) was added 129699.doc: to this solution (referred to as solution b))t. The solution side 10 n thus formed was allowed to stand at 8 Torr for 3 hours. 4 b) The concentration of t K2Pda4 n hexadecyl trimethyl sulphate and ascorbic sputum is the same as that in Example 1. Desertification 16 Xuanji San Yinji Syria / K2PcK: U sodium ascorbate / K2pda4 molar ratio is also an example! The molar ratio is the same. Concentration and examples of solution c^K2pdcl4, desert hexadecyl tris-ammonium and sodium ascorbate expressed relative to the amount of K2pdcl4 and desertification-based triterpene introduced during preparation of solution b) The concentration of 1 is the same. The molar ratio of brominated ten/, alkyl-methylammonium/K^Pdcl4 and sodium ascorbate/K2pdCi4 was also the same as that of Example 1. The concentration of the reduced palladium having a zero oxidation number derived from the solution a) and present in the solution 5) was 5 62 χ 1 〇 7 m / liter. The resulting nanoparticles are composed of 74% cubes (morphological factor 0 78), 7 〇/. Rod (morphological factor < 〇·7), 7% polyhedron and i 2% tetrahedron. A TEM photograph is shown in Figure 2. After the solution was reduced in volume by centrifugation, the palladium nanoparticles were deposited on the alumina by dry impregnation. The catalyst formed from the supported nanoparticles was then washed through a Buchner funnel using a 2 x 1 〇〇mi water/ethanol mixture (2 〇 0 / 〇 water / 80 ° / ethanol). The catalyst was then dried overnight at 30 °C. The catalyst B thus prepared contained 0.3% by weight of Is. Example 3: Synthesis of nanoparticles (catalyst C, not according to the invention) which are not primarily loaded with a morphological factor F = 〇78. First, add 12_5 ml of K2pdcl4.3H2 〇129299.doc -32- 1374119 with a concentration of 1〇·3 mol/L of liters to 25 ml of cetyl bromide at a concentration of 15 mol/L. Methyl sulphate in aqueous solution. Then, a 3 mU aqueous solution of boron bismuth sulphate having a cultivating degree of 0.01 m/m was added under stirring. At 3 〇. After stirring for 1 minute, the prepared nanoparticle seed crystal solution a) was allowed to stand for 2 hours. The concentrations in the solution, the desertified hexamethyl methicone and NaBH4 were the same as those in Example 1. The evolution of cetyltrimethylammonium/hPdCU and NaBH4/K2Pda4 molar ratios is also the same as the molar ratio of the examples. ^ miGG mUt degree is 3W3 Mo is very K2PdCl4.3H2 〇 aqueous solution added to the thief under the temperature of 1 〇〇 ml 〇 24 m / liter of desertification of the six dazzling base triterpene in the aqueous solution. After 5 min, 4 ml of a sodium ascorbate solution having a concentration of 0.08 mol/liter was added dropwise. Next, a 36 〇 y solution was added to this solution (referred to as solution b))f. The solution thus formed was stirred for a minimum of (7) min, followed by standing at 5 (TC for 3 hours. In solution b) IPdC丨ρ was filled with hexamethyl-trimethylmethane and anti-scratch ash. The concentrations in Example 1 were the same. The cetyltrimethylammonium bromide/KJdCl4 and sodium ascorbate/K2Pdcl4 molar ratios are also the same as the molar ratio of the examples to β. Relative to the KJdCl4 and cetyltrimethyl bromide introduced during the preparation of solution b) The amount of the ammonium chloride is the same as the concentration of the solution c) + K2Pdcl4, cetyltrimethylammonium bromide and sodium ascorbate. The crust ratio of cetyltrimethylammonium bromide/KJdCl4 and sodium ascorbate/K2Pdcl4 was also the same as that of Example 1. The concentration of reduced palladium having a zero oxidation number derived from solution a) and present in solution C) is 5 62 x 10-7 mol/liter. 129699.doc •33· 1374119 The nanoparticle formed is composed of 58% cube (morphological factor 0.78), 1 1% rod (morphological factor < 0.7), 10% polyhedron and 21% tetrahedron. . After the volume of the solution was reduced by centrifugation, the palladium nanoparticles were deposited on the alumina by dry impregnation. The catalyst formed from the supported nanoparticles was washed through a Buchner funnel using a 2 X 1 〇〇mi water/ethanol mixture (2 Torr/0 water/80% ethanol).

接著將催化劑於30。(：下乾燥隔夜。如此製備之催化劑c 含有0.3重量％鈀。實例4 :具有形態因子F=〇 78之經負載鈀奈米粒子（催化劑 D ’不根據本發明）之合成。首先，將12.5 ml濃度為ι〇-3莫耳/公升之K2pdCl4.3H2〇水溶液添加至25 ml濃度為0.15莫耳/公升之溴化十六烷基三甲基銨水溶液中。接著在攪拌下添加3 ml濃度為〇〇1莫耳/ 公升之硼氫化鈉水溶液。於3(rc下攪拌1〇分鐘後，使已製備之奈米粒子晶種溶液a)靜置2小時β 於溶液aWlPdCl4、溴化十六烷基三甲基銨及NaBH4i /辰度與實例1中的濃度相同。溴化十六烷基三甲基銨/ hPdCl4及NaBIVKJdCl4莫耳比率亦與實例丨之莫耳比率相同。其次，將100 ml濃度為3χ1〇·3莫耳/公升之K2pdci43H2〇水溶液添加至於溫之剛ml Q 24莫耳/公升溪化十六烧基三甲基錢水溶液中。5_後，逐滴添加4mi濃度為〇·08莫耳/公升之抗壞血酸鈉溶液。接著將360 μ1溶液_ 129699.doc •34- 1374119 加至此溶液（稱為溶液b))中。將由此形成之溶液e)授摔ι〇 min，接著於6(rC下靜置3小時。於溶液b)tK2PdCl4、漠]匕十六统基三甲基録及抗壞血酸鈉之濃度與實例1中的濃度相同。溴化十六烷基三甲基銨/LPdCU及抗壞血酸鈉/K：2Pdcu莫耳比率與實例1之莫耳比率相同。相對於在製備溶液b)期間引入之K2Pdc丨4及溴化十六烷基三甲基叙量表示的於溶液e)fK2Pdcl4、漠化十六烧基三甲基敍及抗壞血酸納之濃度與實例！之濃度㈣。漠化十六烷基三甲基銨/K^Pdcu、抗壞血酸鈉/K2pdcl4莫耳比率亦與實例1之莫耳比率相同。源自溶㈣且存在於溶液c) 中之具有0氧化數的還原鈀之濃度為5 62χ1〇.7莫耳/公升。所形成之奈米粒子係由62%立方體（形態因子為0 78)、 11%棒狀物（形態因子<0·7)、10%多面體及17%四面體構成。The catalyst was then passed at 30. (The next drying was overnight. The catalyst c thus prepared contained 0.3% by weight of palladium. Example 4: Synthesis of supported palladium nanoparticles having a form factor F = 〇78 (catalyst D' not according to the invention). First, 12.5 An aqueous solution of K2pdCl4.3H2 at a concentration of ι〇-3 mol/liter is added to 25 ml of a 0.15 mol/L aqueous cetyltrimethylammonium bromide solution, followed by the addition of 3 ml of concentration under stirring. It is a 1 molar/liter liter aqueous solution of sodium borohydride. After stirring for 3 minutes at 3 rc, the prepared nanoparticle seed solution a) is allowed to stand for 2 hours β in solution aWlPdCl4, brominated sixteen The alkyltrimethylammonium and NaBH4i/min are the same concentrations as in Example 1. The cetyltrimethylammonium bromide/hPdCl4 and NaBIVKJdCl4 molar ratios are also the same as the molar ratio of the examples. The K2pdci43H2 hydrazine aqueous solution having a concentration of 3χ1〇·3 mol/liter is added to Wenzhigang ml Q 24 mol/liter liter of hexadecyl trimethyl hydrazine aqueous solution. After 5 _, the concentration of 4 mi is added dropwise. 〇·08 mol/litre sodium ascorbate solution. Then 360 μ1 solution _ 1296 99.doc •34– 1374119 Add to this solution (called solution b)). The thus formed solution e) was given 〇min, followed by standing at 6 (rC for 3 hours. In solution b) tK2PdCl4, 匕匕匕统三三及 and the concentration of sodium ascorbate and Example 1 The concentration is the same. The cetyltrimethylammonium bromide/LPdCU and sodium ascorbate/K:2Pdcu molar ratios were the same as those of Example 1. Concentrations and examples of solution e) fK2Pdcl4, desertified hexamethyl sulphate and ascorbate expressed in terms of K2Pdc丨4 and cetyltrimethyltrimethyl bromide introduced during preparation of solution b) ! The concentration (four). The crust ratio of cetyltrimethylammonium/K^Pdcu, sodium ascorbate/K2pdcl4 was also the same as that of Example 1. The concentration of reduced palladium having a zero oxidation number derived from solution (iv) and present in solution c) was 5 62 χ 1 〇 7. 7 m / liter. The resulting nanoparticles were composed of 62% cubes (morphological factor 0 78), 11% rods (morphological factor < 0·7), 10% polyhedron and 17% tetrahedron.

在藉由離心減小溶液c)之體積後，藉由乾式浸潰使鈀奈米粒子沈積於氧化鋁上。接者經由布氏漏斗，使用2x100 ml水/乙醇混合物（20% 水/80%乙醇）洗滌由該等經負載奈米粒子形成之催化劑。接著將催化劑於30。〇下乾燥隔夜。如此製備之催化劑D 含有〇·3重量％纪。實例5·具有形態因子F=〇.78之經負載鈀奈米粒子（催化劑 E ’不根據本發明）之合成9 首先’將12.5 1111濃度為10-3莫耳/公升之1(：2]?£}(：14.3112〇水 129699.doc •35· 1374119 溶液添加至25 ml濃度為015莫耳/公升之溴化十六烷基三甲基銨水溶液中。接著在攪拌下添加3 ml濃度為〇〇1莫耳/ 公升之硼氫化鈉水溶液。於30〇c下攪拌1〇分鐘後，使已製備之奈米粒子晶種溶液a)靜置2小時。於溶液a)中KJdCl4、溴化十六烷基三甲基銨及NaBH4i 濃度與實例1中的濃度相同。溴化十六烷基三甲基銨/ K^PdCU及NaBHJK^PdCl4比率亦與實例丨之比率相同。After the volume of the solution c) was reduced by centrifugation, the palladium nanoparticles were deposited on the alumina by dry impregnation. The catalyst formed from the supported nanoparticles was washed with a 2x100 ml water/ethanol mixture (20% water/80% ethanol) via a Buchner funnel. The catalyst was then passed at 30. Dry underarms overnight. The catalyst D thus prepared contained 〇·3 wt%. Example 5 Synthesis of Supported Palladium Nanoparticles with Form Factor F = 〇78 (Catalyst E' Not According to the Invention) 9 First '12.5 1111 Concentration 10-3 Molar/Liter 1 (:2) ?£}(:14.3112〇水129699.doc •35·1374119 The solution was added to 25 ml of a 015 mol/liter hexadecyltrimethylammonium bromide aqueous solution. Then 3 ml of the concentration was added with stirring. 〇〇 1 mol / liter of aqueous sodium borohydride solution. After stirring at 30 ° C for 1 Torr, the prepared nanoparticle seed solution a) was allowed to stand for 2 hours. In solution a) KJdCl4, bromination The concentrations of cetyltrimethylammonium and NaBH4i were the same as those in Example 1. The ratio of cetyltrimethylammonium bromide / K^PdCU and NaBHJK^PdCl4 was also the same as the ratio of the examples.

其次，將100 ml濃度為3xl〇-3莫耳/公升之K2pdCi4.3H2〇水溶液添加至.於90°C下恆溫之1〇〇 mi 0.24莫耳/公升溴化十六烷基二甲基銨水溶液中。5 min後，逐滴添加4 ml濃度為〇.〇8莫耳/公升之抗壞血酸鈉溶液◊接著將36〇 μ1溶液勾添加至此溶液（稱為溶液b))甲。將由此形成之溶液c)攪拌1〇 min ’接著於90°C下靜置3小時。Next, add 100 ml of a 3xl〇-3 mol/L K2pdCi4.3H2 hydrazine aqueous solution to a constant temperature of 1〇〇mi 0.24 mol/L of cetyldimethylammonium bromide at 90 °C. In an aqueous solution. After 5 min, 4 ml of a sodium ascorbate solution having a concentration of 〇.〇8 mol/liter was added dropwise, and then a 36 〇 μ1 solution was added to the solution (referred to as solution b)). The thus formed solution c) was stirred for 1 〇 min ' and then allowed to stand at 90 ° C for 3 hours.

於溶液b)中KJdCU、溴化十六烷基三甲基銨及抗壞血酸鈉之濃度與實例1中的濃度相同。溴化十六烷基三甲基錄/KsPdCU及抗壞血酸鈉/K^PdCU莫耳比率與實例1之莫耳比率相同。相對於在製備溶液b)期間引入之Kjdc!4及溴化十六院基三曱基銨之量表示的於溶液c)中K^PdCU、溴化十六烧基三甲基錄及抗壞血酸鈉之濃度與實例1之濃度相同β漠化十六烷基三甲基銨/KzPdCl4及抗壞血酸鈉/K；2Pdci4莫耳比率亦與實例1之莫耳比率相同。源自溶液a)且存在於溶液勾中之具有〇氧化數的還原纪之濃度為5.62x1 0_7莫耳/公升。所形成之奈米粒子具有68%立方體（形態因子為〇 78)、 129699.doc •36- 1374119 14%棒狀物（形態因子< 〇 7)、1〇〇/〇多面體及8%四面體。在藉由離心減小溶液勹之體積後，藉由乾式浸潰使鈀奈米粒子沈積於氧化鋁上。接著經由布氏漏斗，使用2x100 ml水/乙醇混合物（20% 水/80%乙醇）洗滌由該等經負載奈米粒子形成之催化劑。接著將催化劑於3(TC下乾燥隔夜。如此製備之催化劑E 含有0.3重量％鈀。The concentrations of KJdCU, cetyltrimethylammonium bromide and sodium ascorbate in solution b) were the same as those in Example 1. The molar ratio of cetyltrimethyl bromide/KsPdCU and sodium ascorbate/K^PdCU was the same as that of Example 1. K^PdCU, hexadecyl bromide and sodium ascorbate in solution c) relative to the amount of Kjdc!4 and hexadecane trimethylammonium bromide introduced during preparation of solution b) The concentration was the same as that of Example 1. β cetyltrimethylammonium/KzPdCl4 and sodium ascorbate/K; 2Pdci4 molar ratio was also the same as the molar ratio of Example 1. The concentration of the reducing group derived from the solution a) and present in the solution hook having a ruthenium oxidation number was 5.62 x 1 0_7 mol/liter. The formed nanoparticle has 68% cube (morphological factor 〇78), 129699.doc • 36-1374119 14% rod (morphological factor < 〇7), 1〇〇/〇 polyhedron and 8% tetrahedron . After the volume of the solution was reduced by centrifugation, the palladium nanoparticles were deposited on the alumina by dry impregnation. The catalyst formed from the supported nanoparticles was then washed through a Buchner funnel using 2 x 100 ml water/ethanol mixture (20% water / 80% ethanol). The catalyst was then dried overnight at 3 (TC). The catalyst E thus prepared contained 0.3% by weight of palladium.

實例6:主要為具有a/6之截斷（亦即形態因子F=〇 8〇)之經負載鈀奈米粒子（催化劑F,根據本發明）的合成。首先，將12.5 ml濃度為1〇-3莫耳/公升之K2PdCir3ii2〇水溶液添加至25 ml濃度為〇.15莫耳/公升之溴化十六烷基三曱基銨水溶液中。接著在攪拌下添加3 ml濃度為〇.〇1莫耳/ 公升之硼氫化鈉水溶液。於儿^下攪拌1〇分鐘後，使已製備之奈米粒子晶種溶液a)靜置2小時。Example 6: Synthesis of mainly supported palladium nanoparticles (catalyst F, according to the invention) having a cutoff of a/6 (i.e., form factor F = 〇 8 。). First, 12.5 ml of a K2PdCir3ii2 aqueous solution having a concentration of 1〇-3 mol/liter was added to 25 ml of an aqueous solution of cetyltrimethylammonium bromide having a concentration of 1515 mol/liter. Then, 3 ml of an aqueous solution of sodium borohydride having a concentration of 〇.〇1 mol/liter was added under stirring. After stirring for 1 minute, the prepared nanoparticle seed crystal solution a) was allowed to stand for 2 hours.

於溶液a)中iPdCU之濃度為3.08xl0-4 M ;溴化十六烷基三T基銨之濃度為0·0925 M ;還原劑NaBH4之濃度為 7.4x10 4 Μ，從而得到3〇〇之溴化十六烷基三甲基銨/ LPdCl4莫耳比率及2 4之NaBH4/K2Pdcl4莫耳比率。其次，將100 ml濃度為3xl〇-3莫耳/公升之K2PdcU3^〇水溶液添加至於72t下值溫^⑹Q 24莫耳/公升漠化十 ’、院基—甲基錢水溶液中。5 min後逐滴添加4如濃度為 0.08莫耳/公升之抗壞血酸鈉溶液。接著將綱此容液&)添加至此溶液（稱為溶液b))中。將由此形成之溶液⑽㈣ min ’接著於72t下靜置48小時。 129699.doc •37· 1374119 於溶液b)令K2PdCl4之濃唐Α147χ1λ·3 x A 4之晨度為1.47X10 M;漠化十六烷土一甲基知之遭度為0.1176 Μ.括掠A**/· M，抗壞血醆鈉還原劑之濃度為1.568M03 M，亦即追仆_|__>_々甘_ 臭化十，、烷基三甲基銨/K2PdCU莫耳比率為80’且抗壞錢鈉/K2Pda4莫耳比率為1G67。、The concentration of iPdCU in solution a) is 3.08xl0-4 M; the concentration of cetyltrimethyl bromide bromide is 0·0925 M; the concentration of reducing agent NaBH4 is 7.4×10 4 Μ, thereby obtaining 3〇〇 Cetyltrimethylammonium bromide / LPdCl4 molar ratio and 24 NaBH4/K2Pdcl4 molar ratio. Next, 100 ml of a 3xl 〇-3 mol/L K2PdcU3 〇 aqueous solution was added to a 72 t lower temperature (6) Q 24 mol/litre desertification ten', hospital-methyl alcohol solution. After 5 min, 4 ascorbic acid sodium solution having a concentration of 0.08 mol/liter was added dropwise. This solution is then added to this solution (referred to as solution b)). The thus formed solution (10) (tetra) min ' was then allowed to stand at 72 t for 48 hours. 129699.doc •37· 1374119 In the solution b), the morning of K2PdCl4 is 1.47X10 M, and the degree of the methamphetamine monomethyl is 0.1176 Μ. */· M, the concentration of anti-ascorbic acid sodium reducing agent is 1.568M03 M, that is, the servant _|__>_々甘_ 臭化十, alkyl trimethylammonium / K2PdCU molar ratio is 80' And the anti-bad sodium/K2Pda4 molar ratio is 1G67. ,

於溶液Ο中K2PdCl4之濃度（相對於在製備溶液b)期間引入之K2PdCl4量定義）為1 467χ1〇·3 M;漠化十六烧基三甲基銨之濃度(相對於在製備溶液b)期間引入之溴化十六烷基三甲基銨量的比率定義）為G1174 M;抗壞血酸納還原^ 之濃度為1·568Χ10·3 M’從而得雜03之演化十六烧基三甲基知/K2PdCl4莫耳比率及！〇69之抗壞企酸鈉/K2Pdcl^ 耳比率。所形成之奈米粒子係由75%具有a/6截斷（形態因子為 0.80)之立方體、11%(形態因子<〇 7)及14%多面體構成。在藉由離心減小溶液〇之體積後，藉由乾式浸潰使鈀奈米粒子沈積於氧化紹上。接著經由布氏漏斗，使用2x100 ml水/乙醇混合物（20% 水/80%乙醇）洗滌由該等經負載奈米粒子形成之催化劑。接著將催化劑於30。〇下乾燥隔夜。如此製備之催化劑F 含有0.3重量％鈀。實例7 .對1，3_ 丁二稀氫化之催化測試 1，3 - 丁二稀氫化係在充分攪拌"格林納（Grignard)”型批式反應器中於液相（正庚烷）中，於總氫氣壓力下且於2〇。〇之恆溫溫度下進行。藉由氣相層析分析反應產物。藉由監測壓降來測定以.每公克金屬每分鐘^之莫耳數表示的催化活 129699.doc •38· 性。此等活性報導於夺i 丁稀）表示為初始對應二。將選擇性叫义丁二稀仰- 速率與接著對應於、;肖氫化為h 丁稀之H2消耗的仏消耗速率之比率，轉化為丁炫之1-丁稀之出消耗丁烯相對於丁烯(1(1 丁烯)選擇性對應於所形成之卜 i飞丁 _咕丁烯）之總數的比例，其係於丁一烯之80%轉化 I, φ ^ , 柑置測。測試之前，於5(rc下於虱中預處理催化劑。表1 :根據1，3 -丁-祕為儿1 活性差耳/分鐘/公弟.合辱選擇性選擇性 (1-丁稀）The concentration of K2PdCl4 in the solution enthalpy (defined relative to the amount of K2PdCl4 introduced during preparation of solution b) is 1 467 χ 1 〇 · 3 M; the concentration of desertified hexadecyl trimethylammonium (relative to the preparation of solution b) The ratio of the amount of cetyltrimethylammonium bromide introduced during the period is defined as G1174 M; the concentration of sodium ascorbate reduction is 1.568Χ10·3 M', so that the evolution of misc 03 is 16 /K2PdCl4 molar ratio and! 〇69 anti-bad acid sodium / K2Pdcl ^ ear ratio. The formed nanoparticles were composed of 75% cubes with a/6 cutoff (morphological factor 0.80), 11% (morphological factor < 〇 7) and 14% polyhedron. After the volume of the solution was reduced by centrifugation, the palladium nanoparticles were deposited on the oxide by dry impregnation. The catalyst formed from the supported nanoparticles was then washed through a Buchner funnel using 2 x 100 ml water/ethanol mixture (20% water / 80% ethanol). The catalyst was then passed at 30. Dry underarms overnight. The catalyst F thus prepared contained 0.3% by weight of palladium. Example 7. Catalytic test for 1,3 - butadiene hydrogenation 1,3 - butyl dihydrogenation in a well stirred "Grignard" batch reactor in liquid phase (n-heptane), The reaction product was analyzed by gas chromatography at a total hydrogen pressure and at a constant temperature of 2 Torr. The catalytic activity represented by the number of moles per minute of metal per minute was determined by monitoring the pressure drop. 129699.doc •38· Sex. These activities are reported as the first corresponding two. The selectivity is called Dingdi Rising-rate and then corresponding to; H. hydrogenation to h dilute H2 consumption The ratio of the rate of enthalpy consumption is converted to the ratio of the number of butadiene-derived butenes relative to the butene (1 (1 butene) selectivity corresponding to the total number of formed i-butylene-butenes) It is based on 80% conversion of I, φ ^ , and citrus. Before the test, the catalyst was pretreated in sputum at 5 (rc). Table 1: According to 1,3 - butyl-secret Poor ear / minute / male brother. Insult selective selectivity (1-butan)

_____:氫化量測之活性及選擇性催化劑A、(其中pd奈求粒子主要呈立方體或截頂立方體之形態（比例>70數目％))對於U3· 丁二稀氯化具有優於催化劑C、D、E(其中呈立方體形態奈米粒子之比例小於70數目％)的催化活性（每公克鈀）、選擇性…，3-丁二稀）叫1· 丁歸）及！-丁烯選擇性。因此，除使用本發明之方法製備之催化劑A、B及F比催化劑C、〇及£更具活性的優點外，此等三種催化劑A、B&F還對單烯烴（1_丁烯）比對飽和產物（丁烷）更具選擇性，此由對於催化劑A、b&f 而言高達兩倍之k(l，3· 丁二烯）/k(1_ 丁烯）選擇性所證明。其還對1-丁烯異構體比對2-丁烯異構體更具選擇性，此由 1 - 丁烯選擇性所示。 129699.doc .39· 1374119 【圖式簡單說明】圖1展示根據實例1之催化劑A之TEM相片。圖2展示根據實例2之催化劑B之TEM相片。_____: Hydrogenation activity and selective catalyst A, (where pd is mainly in the form of cubes or truncated cubes (ratio > 70% by number)) is superior to catalyst C for U3· butyl dichloride , D, E (in which the proportion of cube-shaped nanoparticles is less than 70% by number), the catalytic activity (per gram of palladium), selectivity..., 3-butadiene) is called 1 · Dinggui) and! - Butene selectivity. Thus, in addition to the advantages of catalysts A, B and F prepared by the process of the invention being more active than catalysts C, 〇 and £, these three catalysts A, B & F also have a monoolefin (1-butene) ratio More selective for the saturated product (butane), as evidenced by up to twice the selectivity of k(l,3·butadiene)/k(1 -butene) for Catalysts A, b&f. It is also more selective for the 1-butene isomer than for the 2-butene isomer, as indicated by the 1-butene selectivity. 129699.doc .39· 1374119 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a TEM photograph of Catalyst A according to Example 1. 2 shows a TEM photograph of Catalyst B according to Example 2.

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Claims

1374119 十公告本j 申請專利念菌一~1 第097111128號專利申請宰中文节镇專利箱‘幸(101年3 私日修正本一種製備包含載體及立方金屬^米粒子$_催化劑之·万法，該方法至少包含下列步驟： a) 製備至少一種水性溶液，其含有至少一種選自銻、録、鐵、釕、鉑、鈀及銥之金屬的至少-個來源、至少一種還原劑R1及至少一種穩定劑； b) 於嚴格高於70°C且小於或等於80°C之溫度下製備至少一種水性溶液，其含有至少一種選自鎳、鈷、鐵' 釘、銘、鈀及銥之金屬的至少一個來源及至少一種穩定劑； c) 在至少一種還原劑R2存在下，將步驟a)中獲得之該水 !生/谷液與步驟b)中獲得之該水性溶液混合以獲得呈立方形態之金屬奈米粒子’其佔所形成之金屬奈米粒子之全部數量的至少70數目％ ; d) 使源自步驟c)之該等金屬奈米粒子沈積於該載體上，其中該還原劑R1及R2係選自氫、肼、羥胺、鹼金屬硼氫化物及氬化物、羧酸、醇、多元醇、醛、酮及其離子’且該穩定劑係一包含鹵化四級敍鹽之界面活性劑。如β求項1之方法’其包含繼該步驟d)後的至少一個步驟 e) ，其由洗滌該等經負載奈米粒子組成。 3 i- .如吻求項1之方法，其中該等立方金屬奈米粒子之面之邊的長度係在範圍2 nm至200 nm内。 4·如睛求項1之方法，其中該等製備得之立方單金屬奈米 129699-1010312.doc 1374119 粒子係由把構成。 5. 如請求項1之方法，其中藉由引入第汨族金屬之來源以進行步驟a)及/或步騍b)而製備得立方雙金屬奈米粒子。 6. 如請求項1之方法，其中該還原劑尺2係經引入至在該步驟b)之過程中製備得之該水性溶液中或經引入至由將步驟a)中獲得之該水性溶液與步驟b)中獲得之該水性溶液混合產生的溶液中。 7. 如明求項1之方法，其中該還原劑R1為化合物NaBH4。 8. 如請求項1之方法，其中該還原劑R2為抗壞血酸鈉。 9. 如凊求項1之方法，其中用於進行步驟a)及步驟…之該界面活性劑為溴化十六烷基三甲基銨。 10. 如响求項1之方法，其中在該步驟幻結束時獲得之該水性 '合液中，界面活性劑/金屬莫耳比率係在範圍1至1000内且引入步驟a)之Rl/金屬莫耳比率係在範圍1至3〇内。 11. 如清求項1之方法，其中在該步驟…結束時獲得之該水性溶液中，界面活性劑/金屬莫耳比率係在範圍5至500内。 12. 如請求頂^ , 法’其中該步驟C)係於與進行該步驟b)相同之溫度下進行。 13. 如請求項1之古、i 心不在，其中在步驟c)之該混合物中，相對於 •經引入以進行該步驟b)之金屬量定義的金屬之濃度係在範圍1 X 10·5莫写1 /八、耳/a升至1莫耳/公升内，經定義為引入步驟）中、之穩&劑量之比率的穩定劑之濃度係在範圍0 ^ 、耳A升至1莫耳/公升内’且還原劑R2之濃度係在範圍 1X10-5莫耳/公升至旧耳/公升内。 J 29699-1010312.doc 1374119 14.如請求項1之方法，其中用於進行該步驟d)之該載體為氧化鋁、二氧化矽或二氧化矽-氧化鋁。 1 5. —種選擇性氫化不飽和烴之方法，其係在使用如請求項 1之方法製備之催化劑存在下進行。1374119 Ten Announcement Ben j Patent application No.1~1 No. 097111128 Patent application for slaughtering Chinese town patent box 'Fortunately (101 years 3 private day revision) A preparation containing carrier and cubic metal ^ rice particles $_catalyst The method comprises at least the following steps: a) preparing at least one aqueous solution containing at least one source selected from the group consisting of ruthenium, ruthenium, iron, ruthenium, platinum, palladium and iridium, at least one reducing agent R1 and at least a stabilizer; b) at least one aqueous solution containing at least one metal selected from the group consisting of nickel, cobalt, iron, nail, palladium, and rhodium, at a temperature strictly above 70 ° C and less than or equal to 80 ° C At least one source and at least one stabilizer; c) mixing the water obtained in step a) with the aqueous solution obtained in step b) in the presence of at least one reducing agent R2 to obtain a cubic Forming the metal nanoparticle 'which is at least 70% by number of the total number of metal nanoparticles formed; d) depositing the metal nanoparticles derived from step c) onto the support, wherein the reducing agent R1 R2 is selected from the group consisting of hydrogen, hydrazine, hydroxylamine, alkali metal borohydrides and hydrides, carboxylic acids, alcohols, polyols, aldehydes, ketones and their ions' and the stabilizer is a surfactant comprising a halogenated quaternary salt . The method of [beta]1, which comprises at least one step e) following the step d), consists of washing the loaded nanoparticles. 3 i- . The method of claim 1, wherein the sides of the faces of the cubic metal nanoparticles are in the range of 2 nm to 200 nm. 4. The method of claim 1, wherein the prepared cubic single metal nano 129699-1010312.doc 1374119 particle system is composed of a handle. 5. The method of claim 1, wherein the cubic bimetallic nanoparticle is prepared by introducing a source of the thorium metal to carry out step a) and/or step b). 6. The method of claim 1, wherein the reducing agent 2 is introduced into the aqueous solution prepared in the process of the step b) or introduced into the aqueous solution obtained by the step a) The aqueous solution obtained in step b) is mixed in a solution produced. 7. The method of claim 1, wherein the reducing agent R1 is the compound NaBH4. 8. The method of claim 1, wherein the reducing agent R2 is sodium ascorbate. 9. The method of claim 1, wherein the surfactant used to perform step a) and step ... is cetyltrimethylammonium bromide. 10. The method of claim 1, wherein in the aqueous 'liquid mixture obtained at the end of the step, the surfactant/metal molar ratio is in the range of 1 to 1000 and is introduced into the R1/metal of step a) The molar ratio is in the range of 1 to 3 Torr. 11. The method of claim 1, wherein the surfactant/metal molar ratio in the aqueous solution obtained at the end of the step is in the range of 5 to 500. 12. If the request top, the method 'where the step C) is carried out at the same temperature as the step b). 13. If the claim 1 is ancient, i is absent, wherein in the mixture of step c), the concentration of the metal relative to the metal amount introduced to carry out the step b) is in the range 1 X 10·5 Mo written 1 / 八, ear / a rose to 1 m / liter, defined as the ratio of stabilizer and dose ratio in the introduction step), the concentration of the stabilizer is in the range 0 ^, the ear A rises to 1 Mo The concentration of the reducing agent R2 in the ear/liter is in the range of 1X10-5 m/d to the old ear/liter. The method of claim 1, wherein the carrier for carrying out the step d) is alumina, ceria or cerium oxide-alumina. A method for selectively hydrogenating an unsaturated hydrocarbon which is carried out in the presence of a catalyst prepared by the method of claim 1.

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